JP3241889B2 - Method for producing cyanoacylcyclopropane compound and 2-cyanoacyl-4-butanolide compound used therefor - Google Patents
Method for producing cyanoacylcyclopropane compound and 2-cyanoacyl-4-butanolide compound used thereforInfo
- Publication number
- JP3241889B2 JP3241889B2 JP23545893A JP23545893A JP3241889B2 JP 3241889 B2 JP3241889 B2 JP 3241889B2 JP 23545893 A JP23545893 A JP 23545893A JP 23545893 A JP23545893 A JP 23545893A JP 3241889 B2 JP3241889 B2 JP 3241889B2
- Authority
- JP
- Japan
- Prior art keywords
- compound
- general formula
- group
- butanolide
- represented
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 150000001875 compounds Chemical class 0.000 title claims description 43
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- WEVYAHXRMPXWCK-UHFFFAOYSA-N methyl cyanide Natural products CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 19
- -1 butanolide compound Chemical class 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical class O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 7
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 239000005749 Copper compound Substances 0.000 claims description 5
- 125000003545 alkoxy group Chemical group 0.000 claims description 5
- 150000001880 copper compounds Chemical class 0.000 claims description 5
- 125000004414 alkyl thio group Chemical group 0.000 claims description 4
- 125000005110 aryl thio group Chemical group 0.000 claims description 4
- 125000004104 aryloxy group Chemical group 0.000 claims description 4
- 238000006114 decarboxylation reaction Methods 0.000 claims description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 4
- 229910001516 alkali metal iodide Inorganic materials 0.000 claims description 3
- 238000006722 reduction reaction Methods 0.000 claims description 3
- 238000007157 ring contraction reaction Methods 0.000 claims 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 125000004432 carbon atom Chemical group C* 0.000 description 13
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- 239000002585 base Substances 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- 239000000203 mixture Substances 0.000 description 9
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 7
- 239000012312 sodium hydride Substances 0.000 description 7
- 229910000104 sodium hydride Inorganic materials 0.000 description 7
- BWZVCCNYKMEVEX-UHFFFAOYSA-N 2,4,6-Trimethylpyridine Chemical compound CC1=CC(C)=NC(C)=C1 BWZVCCNYKMEVEX-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- RTWBVSGOEXKMRE-UHFFFAOYSA-N 3-(1-ethylcyclopropyl)-3-oxopropanenitrile Chemical compound CCC1(CC1)C(=O)CC#N RTWBVSGOEXKMRE-UHFFFAOYSA-N 0.000 description 4
- 229910021595 Copper(I) iodide Inorganic materials 0.000 description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 description 4
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(i) oxide Chemical compound [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 239000004009 herbicide Substances 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- AUHZEENZYGFFBQ-UHFFFAOYSA-N 1,3,5-Me3C6H3 Natural products CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 3
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-dimethylpyridine Chemical compound CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000004440 column chromatography Methods 0.000 description 3
- 230000002363 herbicidal effect Effects 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 235000009518 sodium iodide Nutrition 0.000 description 3
- GFYHSKONPJXCDE-UHFFFAOYSA-N sym-collidine Natural products CC1=CN=C(C)C(C)=C1 GFYHSKONPJXCDE-UHFFFAOYSA-N 0.000 description 3
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 description 2
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 2
- FKNQCJSGGFJEIZ-UHFFFAOYSA-N 4-methylpyridine Chemical compound CC1=CC=NC=C1 FKNQCJSGGFJEIZ-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 239000012230 colorless oil Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 2
- QTMDXZNDVAMKGV-UHFFFAOYSA-L copper(ii) bromide Chemical compound [Cu+2].[Br-].[Br-] QTMDXZNDVAMKGV-UHFFFAOYSA-L 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- MLIREBYILWEBDM-UHFFFAOYSA-N cyanoacetic acid Chemical compound OC(=O)CC#N MLIREBYILWEBDM-UHFFFAOYSA-N 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 239000004210 ether based solvent Substances 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- ZCSHNCUQKCANBX-UHFFFAOYSA-N lithium diisopropylamide Chemical compound [Li+].CC(C)[N-]C(C)C ZCSHNCUQKCANBX-UHFFFAOYSA-N 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 235000019341 magnesium sulphate Nutrition 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- RLFIINLNJAZOEG-UHFFFAOYSA-N methyl 3-ethyl-2-oxooxolane-3-carboxylate Chemical compound COC(=O)C1(C(=O)OCC1)CC RLFIINLNJAZOEG-UHFFFAOYSA-N 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- XWKFPIODWVPXLX-UHFFFAOYSA-N 2-methyl-5-methylpyridine Natural products CC1=CC=C(C)N=C1 XWKFPIODWVPXLX-UHFFFAOYSA-N 0.000 description 1
- SDARMQNRQJBGQE-UHFFFAOYSA-N 3-cyclopropyl-3-oxopropanenitrile Chemical class N#CCC(=O)C1CC1 SDARMQNRQJBGQE-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 229910021589 Copper(I) bromide Inorganic materials 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 229910021590 Copper(II) bromide Inorganic materials 0.000 description 1
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 1
- LVZWSLJZHVFIQJ-UHFFFAOYSA-N Cyclopropane Chemical compound C1CC1 LVZWSLJZHVFIQJ-UHFFFAOYSA-N 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 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
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 229910001508 alkali metal halide Inorganic materials 0.000 description 1
- 150000008045 alkali metal halides Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000005116 aryl carbamoyl group Chemical group 0.000 description 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 229910000009 copper(II) carbonate Inorganic materials 0.000 description 1
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 description 1
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 description 1
- GBRBMTNGQBKBQE-UHFFFAOYSA-L copper;diiodide Chemical compound I[Cu]I GBRBMTNGQBKBQE-UHFFFAOYSA-L 0.000 description 1
- 239000011646 cupric carbonate Substances 0.000 description 1
- 235000019854 cupric carbonate Nutrition 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- CEIPQQODRKXDSB-UHFFFAOYSA-N ethyl 3-(6-hydroxynaphthalen-2-yl)-1H-indazole-5-carboximidate dihydrochloride Chemical group Cl.Cl.C1=C(O)C=CC2=CC(C3=NNC4=CC=C(C=C43)C(=N)OCC)=CC=C21 CEIPQQODRKXDSB-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- HVTICUPFWKNHNG-UHFFFAOYSA-N iodoethane Chemical compound CCI HVTICUPFWKNHNG-UHFFFAOYSA-N 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Furan Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【0001】[0001]
【産業上の利用分野】本発明は、カラー写真感光材料用
イエローカプラーまたは除草剤を工業的規模で製造する
際に有用なシクロプロパン化合物の製造方法とそれに用
いる新規な2−シアノアシル−4−ブタノリド化合物に
関する。The present invention relates to a process for producing a cyclopropane compound useful for producing a yellow coupler or a herbicide for a color photographic light-sensitive material on an industrial scale, and a novel 2-cyanoacyl-4-butanolide used therefor. For compounds.
【0002】[0002]
【従来の技術】シアノアセチルシクロプロパン化合物は
既に公知であり(EP496631A1;EP4966
30A1;GB2141712A1;US450034
5;EP129408A2、EP129928A1;D
E3209472A1)、除草剤として用いられる化合
物の合成中間体である。また、シアノアセチルシクロプ
ロパン化合物は、例えば特開平4−218042に記載
されているシクロプロパン骨格を有するカラー写真感光
材料用のイエローカプラーの合成中間体として有用であ
る。(シアノ基は、イミダート基に変換後、さらにアニ
リンとの反応により、アリールカルバモイル基に変換さ
れ、イエローカプラーに導かれる。)2. Description of the Related Art Cyanoacetylcyclopropane compounds are already known (EP496631A1; EP4966).
30A1; GB2417712A1; US450034
5; EP129408A2, EP129998A1; D
E3209472 A1), a synthetic intermediate for compounds used as herbicides. The cyanoacetylcyclopropane compound is useful as a synthetic intermediate of a yellow coupler for a color photographic light-sensitive material having a cyclopropane skeleton described in, for example, JP-A-4-218042. (The cyano group is converted to an imidate group, and further converted to an arylcarbamoyl group by reaction with aniline, leading to a yellow coupler.)
【0003】従来、シアノアセチルシクロプロパン化合
物は以下に示すように、アルキルシクロプロパンカルボ
ン酸化合物と活性メチレン化合物(シアノ酢酸、アセト
ニトリルなど)との縮合反応により得られているが、Conventionally, a cyanoacetylcyclopropane compound has been obtained by a condensation reaction between an alkylcyclopropanecarboxylic acid compound and an active methylene compound (cyanoacetic acid, acetonitrile, etc.) as shown below.
【0004】[0004]
【化6】 Embedded image
【0005】出発原料となるシクロプロパンカルボン酸
化合物を高収率で、短かい工程で工業的に製造すること
が難しく、種々の改良が試みられている。代表的な方法
を下記に示す。[0005] It is difficult to industrially produce a cyclopropanecarboxylic acid compound as a starting material in a high yield and in a short process, and various improvements have been attempted. A typical method is shown below.
【0006】[0006]
【化7】 Embedded image
【0007】一方、以下に示すように、ある種のアルカ
リ金属のハロゲン化物(例えばヨウ化ナトリウム、塩化
リチウム)を用いてヘキサメチルホスホリックアミド
(HMPA)のような非プロトン性極性溶媒中反応を行
うことによって、γ−ブチロラクトンからシクロプロパ
ンへの脱炭酸環縮小反応が達成できることが知られてい
るが(Chemistry Letters, 1149(1975) )、反応温度が
160〜180℃と高温であり、そのため、製造装置と
して高温反応が可能なものを用いる必要があるなど省エ
ネルギー、製造装置のコストなどの点で改良を必要とす
る合成プロセスである。On the other hand, as shown below, a certain alkali metal halide (eg, sodium iodide, lithium chloride) is used to react in an aprotic polar solvent such as hexamethylphosphoric amide (HMPA). By performing the reaction, it is known that a decarboxylation ring reduction reaction from γ-butyrolactone to cyclopropane can be achieved (Chemistry Letters, 1149 (1975)), but the reaction temperature is as high as 160 to 180 ° C. This is a synthesis process that requires improvement in terms of energy saving, cost of the manufacturing apparatus, etc., such as the need to use a manufacturing apparatus capable of high-temperature reaction.
【0008】[0008]
【化8】 Embedded image
【0009】[0009]
【発明が解決しようとする課題】本発明の目的は、安価
で入手容易な化合物から合成できる化合物を出発原料と
し、短工程で、カラー写真用イエローカプラー、除草剤
などの合成中間体として有用であるシアノアシルシクロ
プロパン化合物を得る製造方法を提供することにある。
また、本発明の目的はシアノアシルシクロプロパン化合
物を比較的温和な条件下で好収率で得ることができる方
法とそれに用いる2−シアノアシル−4−ブタノリド化
合物を提供することである。SUMMARY OF THE INVENTION An object of the present invention is to use a compound which can be synthesized from an inexpensive and easily available compound as a starting material, and is useful as a synthetic intermediate for a yellow coupler for color photography, a herbicide, etc. in a short process. An object of the present invention is to provide a production method for obtaining a certain cyanoacylcyclopropane compound.
Another object of the present invention is to provide a method capable of obtaining a cyanoacylcyclopropane compound at a high yield under relatively mild conditions, and a 2-cyanoacyl-4-butanolide compound used for the method.
【0010】[0010]
【課題を解決するための手段】上記の目的は、一般式
(I)The object of the present invention is to provide a compound of the formula (I)
【0011】[0011]
【化9】 Embedded image
【0012】(式中、R1 、R2 、R3 、R4 、R5 、
R6 、R7 はそれぞれ水素原子、アルキル基、アリール
基、アルコキシ基、アリールオキシ基、アルキルチオ基
又はアリールチオ基を表わす。)で表わされる2−シア
ノアシル−4−ブタノリド化合物及びこれをピリジン系
溶媒を用い、アルカリ金属ヨウ化物の存在下で脱炭酸環
縮小反応させることを特徴とする一般式(IV)Wherein R 1 , R 2 , R 3 , R 4 , R 5 ,
R 6 and R 7 each represent a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group or an arylthio group. A) general formula (IV), characterized by subjecting a 2-cyanoacyl-4-butanolide compound represented by the formula) and a pyridine-based solvent to a decarboxylation ring reduction reaction in the presence of an alkali metal iodide.
【0013】[0013]
【化10】 Embedded image
【0014】(式中、R1 、R2 、R3 、R4 、R5 、
R6 、R7 は一般式(I)におけるものと同義であ
る。)で表わされるシアノアシルシクロプロパン化合物
の製造方法によって達成された。一般式(I)で表わさ
れる化合物は、一般式(II)Wherein R 1 , R 2 , R 3 , R 4 , R 5 ,
R 6 and R 7 have the same meaning as in formula (I). This was achieved by a method for producing a cyanoacylcyclopropane compound represented by the following formula: The compound represented by the general formula (I) has the general formula (II)
【0015】[0015]
【化11】 Embedded image
【0016】(式中、R1 、R2 、R3 、R4 、R5 は
一般式(I)におけるものと同義であり、R8 はアルキ
ル基を表わす。)で表わされるγ−ブチロラクトン誘導
体と、一般式(III)(Wherein R 1 , R 2 , R 3 , R 4 , and R 5 have the same meanings as those in formula (I), and R 8 represents an alkyl group). And the general formula (III)
【0017】[0017]
【化12】 Embedded image
【0018】(式中、R6 、R7 は一般式(I)におけ
るものと同義である。)で表わされるアセトニトリル化
合物を反応させることによって得ることができる。(Wherein, R 6 and R 7 have the same meanings as those in formula (I)), and can be obtained by reacting an acetonitrile compound represented by the formula:
【0019】以下に本発明の化合物及び製造方法につい
て詳しく説明する。本発明方法は次の反応工程によって
示すことができる。Hereinafter, the compound of the present invention and the production method will be described in detail. The method of the present invention can be illustrated by the following reaction steps.
【0020】[0020]
【化13】 Embedded image
【0021】一般式(I)〜(IV)において、R1 、R
2 、R3 、R4 、R5 、R6 、R7はそれぞれ水素原
子、好ましくは炭素数1〜8のアルキル基(例えばメチ
ル、エチル、プロピル、ベンジル)、好ましくは炭素数
6〜15のアリール基(例えばフェニル、ナフチル)、
好ましくは炭素数1〜8のアルコキシ基(例えばメトキ
シ、エトキシ、2−エチルヘキシルオキシ)、好ましく
は炭素数6〜15のアリールオキシ基(例えばフェノキ
シ、ナフトキシ)、好ましくは炭素数1〜8のアルキル
チオ基(例えばメチルチオ、エチルチオ、ブチルチ
オ)、好ましくは炭素数6〜15のアリールチオ基(例
えばフェニルチオ、ナフチルチオ)を表わし、これらの
置換基はさらに、ハロゲン原子(例えばフッ素原子、塩
素原子、臭素原子、ヨウ素原子)、好ましくは炭素数1
〜8のアルキル基(例えばメチル、エチル、プロピ
ル)、好ましくは炭素数6〜15のアリール基(例えば
フェニル、ナフチル)、好ましくは炭素数1〜8のアル
コキシ基(例えばメトキシ、エトキシ)、ニトロ基、ア
シル基(例えばベンゾイル、アセチル)、シアノ基など
で置換されていてもよい。In the general formulas (I) to (IV), R 1 , R
2 , R 3 , R 4 , R 5 , R 6 , and R 7 are each a hydrogen atom, preferably an alkyl group having 1 to 8 carbon atoms (for example, methyl, ethyl, propyl, benzyl), preferably 6 to 15 carbon atoms. Aryl groups (eg phenyl, naphthyl),
Preferably, it is an alkoxy group having 1 to 8 carbon atoms (e.g., methoxy, ethoxy, 2-ethylhexyloxy), preferably an aryloxy group having 6 to 15 carbon atoms (e.g., phenoxy, naphthoxy), preferably an alkylthio group having 1 to 8 carbon atoms. (E.g., methylthio, ethylthio, butylthio), preferably an arylthio group having 6 to 15 carbon atoms (e.g., phenylthio, naphthylthio), and these substituents further include a halogen atom (e.g., a fluorine atom, a chlorine atom, a bromine atom, an iodine atom). ), Preferably having 1 carbon atom
To 8 alkyl groups (eg, methyl, ethyl, propyl), preferably an aryl group having 6 to 15 carbon atoms (eg, phenyl, naphthyl), preferably an alkoxy group having 1 to 8 carbon atoms (eg, methoxy, ethoxy), a nitro group , An acyl group (for example, benzoyl, acetyl), a cyano group and the like.
【0022】R1 、R2 、R3 、R4 、R5 、R6 、R
7 はさらに好ましくは水素原子、炭素数1〜8のアルキ
ル基、炭素数6〜15のアリール基を表わす。R1 、R
2 、R3 、R4 、R6 、R7 は特に好ましくは水素原子
である。R5 は特に好ましくは炭素数1〜8のアルキル
基である。R8 は好ましくは炭素数1〜8のアルキル基
(例えばメチル、エチル、プロピル)を表わし、特に好
ましくは、メチル基又はエチル基である。次に一般式
(I)の製造方法について説明する。一般式(II)で表
わされるγ−ブチロラクトン誘導体は、次に示す経路に
て、通常の入手可能な化合物より合成できる。R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R
7 more preferably represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an aryl group having 6 to 15 carbon atoms. R 1 , R
2 , R 3 , R 4 , R 6 and R 7 are particularly preferably a hydrogen atom. R 5 is particularly preferably an alkyl group having 1 to 8 carbon atoms. R 8 preferably represents an alkyl group having 1 to 8 carbon atoms (eg, methyl, ethyl, propyl), and particularly preferably a methyl group or an ethyl group. Next, the production method of the general formula (I) will be described. The γ-butyrolactone derivative represented by the general formula (II) can be synthesized from commonly available compounds by the following route.
【0023】[0023]
【化14】 Embedded image
【0024】1または3で表わされるγ−ブチロラクト
ン誘導体は数多く公知例が知られる容易に入手可能な化
合物であり、代表的には、以下の文献の方法に準じて合
成できる。〔Arch. Pharm. 272, 313 (1934); Angew. C
hem. 48, 701 (1935); Ann. 526, 1(1936); J. Am. Che
m. Soc. 64, 557 (1942) など〕The γ-butyrolactone derivative represented by 1 or 3 is a readily available compound having a large number of known examples, and can be typically synthesized according to the method of the following literature. [Arch. Pharm. 272 , 313 (1934); Angew. C
hem. 48 , 701 (1935); Ann. 526 , 1 (1936); J. Am. Che
m. Soc. 64 , 557 (1942) etc.)
【0025】次いで、1または3を塩基存在下、炭酸エ
ステル類(R8 O)2 COと反応させることにより、γ
−ブチロラクトン誘導体(アルコキシカルボニル−4−
ブタノリド誘導体)2(一般式(II)、R5 =H)また
は一般式(II)の化合物へ変換できる。塩基としては、
水素化ナトリウム、カリウム−tert−ブトキシド、
リチウム−ジ−iso−プロピルアミド、炭酸ナトリウ
ム、炭酸カリウム、DBU(1,8−ジアザビシクロ
[5,4,0]−7−ウンデセン)、トリエチルアミン
等があげられ、強塩基である水素化ナトリウム、リチウ
ム−ジ−iso−プロピルアミド等が好ましく、特に水
素化ナトリウムが好ましい。塩基は1または3に対して
0.5〜1.5当量で用いればよい。炭酸エステル類
(R8 O)2COとしては、炭酸ジメチル、炭酸ジエチ
ル等があげられる。炭酸エステル類の使用量は、1また
は3 1モルに対して0.5〜20モル、好ましくは
0.5〜5モルである。反応溶媒としては、トルエンな
どの芳香族炭化水素系溶媒、テトラヒドロフランなどの
エーテル系溶媒が好ましく用いられる。反応温度は0〜
130℃が適当で、20〜100℃が好ましい。2(一
般式(II)、R5 =H)への水素原子以外のR5 の導入
は、2を塩基存在下さらにR5 X(Xはハロゲン原子
(例えば塩素原子)、−OSO2 CH3 、Next, by reacting 1 or 3 with carbonates (R 8 O) 2 CO in the presence of a base, γ
-Butyrolactone derivative (alkoxycarbonyl-4-
Butanolide derivative) 2 (general formula (II), R 5 = H) or compound of general formula (II). As the base,
Sodium hydride, potassium-tert-butoxide,
Lithium-di-iso-propylamide, sodium carbonate, potassium carbonate, DBU (1,8-diazabicyclo [5,4,0] -7-undecene), triethylamine and the like, and strong bases such as sodium hydride and lithium -Di-iso-propylamide and the like are preferred, and sodium hydride is particularly preferred. The base may be used in 0.5 to 1.5 equivalents to 1 or 3 . Examples of the carbonates (R 8 O) 2 CO include dimethyl carbonate, diethyl carbonate and the like. The amount of the carbonate ester to be used is 0.5 to 20 mol, preferably 0.5 to 5 mol per 1 or 31 mol. As the reaction solvent, aromatic hydrocarbon solvents such as toluene and ether solvents such as tetrahydrofuran are preferably used. The reaction temperature is 0
130 ° C is suitable, and 20 to 100 ° C is preferable. 2 (general formula (II), R 5 = H) introduction of R 5 other than hydrogen onto the 2 presence of a base addition R 5 X (X is a halogen atom (e.g. a chlorine atom), - OSO 2 CH 3 ,
【0026】[0026]
【化15】 Embedded image
【0027】などを表わす。)を反応させることで行う
ことができる。ここ用いられる塩基としては、前述のも
のがあげられ、炭酸ナトリウム、炭酸カリウム、DB
U、トリエチルアミン等が好ましい。次いで一般式(I
I)で表わされる化合物は、塩基存在下、一般式(III)
で表わされるアセトニトリル化合物と反応させることに
より、一般式(I)へと導くことができる。一般式(II
I) で表わされるアセトニトリル化合物としては、アセ
トニトリル、プロピオニトリル等があげられる。一般式
(III) の化合物の使用量は、一般式(II)で表わされる
化合物1モルに対し、好ましくは0.1〜5モル、より
好ましくは0.5〜2モルである。塩基としては前述の
ものがあげられ、水素化ナトリウム、金属ナトリウム、
カリウム−tert−ブトキシド、リチウム−ジ−is
o−プロピルアミドなどの強塩基が好ましく、特に水素
化ナトリウムが好ましい。塩基の量としては、一般式(I
II) のアセトニトリル化合物1モルに対して好ましくは
0.5〜2.5モル、より好ましくは0.9〜2.2モ
ル用いられる。反応溶媒としては芳香族炭化水素系溶媒
(例えばベンゼン、トルエン、キシレン)、エーテル系
溶媒(例えばテトラヒドロフラン、1,2−ジメトキシ
エタン、1,4−ジオキサン)が好ましく用いられる。
反応温度は好ましくは0〜150℃、より好ましくは2
0〜120℃である。この反応は、短時に終了し、あま
り長時間行わない方がよい。好ましくは2時間以内であ
り、より好ましくは0.5時間以内である。And so on. ) Can be carried out. Examples of the base used herein include those described above, such as sodium carbonate, potassium carbonate, and DB.
U, triethylamine and the like are preferred. Then, the general formula (I
The compound represented by the formula (I) is represented by the general formula (III) in the presence of a base:
By reacting with an acetonitrile compound represented by the following formula (I), it is possible to lead to the general formula (I). General formula (II
Examples of the acetonitrile compound represented by I) include acetonitrile, propionitrile and the like. General formula
The amount of the compound (III) to be used is preferably 0.1 to 5 mol, more preferably 0.5 to 2 mol, per 1 mol of the compound represented by the general formula (II). Examples of the base include those described above, and sodium hydride, metallic sodium,
Potassium-tert-butoxide, lithium-di-is
A strong base such as o-propylamide is preferred, and sodium hydride is particularly preferred. As the amount of the base, the general formula (I
It is preferably used in an amount of 0.5 to 2.5 mol, more preferably 0.9 to 2.2 mol, per 1 mol of the acetonitrile compound of II). As the reaction solvent, aromatic hydrocarbon solvents (eg, benzene, toluene, xylene) and ether solvents (eg, tetrahydrofuran, 1,2-dimethoxyethane, 1,4-dioxane) are preferably used.
The reaction temperature is preferably 0 to 150 ° C, more preferably 2 to 150 ° C.
0-120 ° C. This reaction should be completed in a short time and not carried out for a very long time. Preferably it is within 2 hours, more preferably within 0.5 hour.
【0028】次に一般式(I)で表わされる2−シアノ
アシル−4−ブタノリド化合物から一般式(IV)で表わ
されるシアノアシルシクロプロパン化合物への変換につ
いて説明する。アルカリ金属ヨウ化物としては、ヨウ化
リチウム、ヨウ化ナトリウム、ヨウ化カリウムが好まし
く用いられ、一般式(I)の2−シアノアシル−4−ブ
タノリド化合物1モルに対して、好ましくは0.1〜2
モル、より好ましくは0.3〜1モル用いられる。ピリ
ジン系溶媒としては、ピリジン、2−メチルピリジン、
4−メチルピリジン、2,6−ルチジン、2,4,6−
コリジン、キノリンが好ましく用いられ、特に2,4,
6−コリジンが好ましく用いられる。この反応において
は、1価又は2価の銅化合物を用いることが反応温度を
低くすることができることから好ましい。1価又は2価
の銅化合物としては、塩化銅(I)、臭化銅(I)、ヨ
ウ化銅(I)、酸化銅(I)、塩化銅(II)、臭化銅
(II)、酢酸銅(II)、炭酸銅(II)などが用いられる
が、好ましくはヨウ化銅(I)、酸化銅(I)が用いら
れ、特に好ましくはヨウ化銅(I)が用いられる。これ
らの銅化合物は一般式(I)の化合物1モルに対して、
好ましくは0.01〜10モル、より好ましくは0.0
5〜1モル用いられる。反応温度としては、好ましくは
100〜150℃、特に好ましくは120〜140℃で
ある。反応時間は0.5〜5時間、好ましくは1〜3時
間である。Next, the conversion of the 2-cyanoacyl-4-butanolide compound represented by the general formula (I) to the cyanoacylcyclopropane compound represented by the general formula (IV) will be described. As the alkali metal iodide, lithium iodide, sodium iodide, and potassium iodide are preferably used, and preferably 0.1 to 2 based on 1 mol of the 2-cyanoacyl-4-butanolide compound of the general formula (I).
Mole, more preferably 0.3 to 1 mole. As the pyridine solvent, pyridine, 2-methylpyridine,
4-methylpyridine, 2,6-lutidine, 2,4,6-
Collidine and quinoline are preferably used.
6-collidine is preferably used. In this reaction, it is preferable to use a monovalent or divalent copper compound because the reaction temperature can be lowered. Examples of the monovalent or divalent copper compound include copper (I) chloride, copper (I) bromide, copper (I) iodide, copper (I) oxide, copper (II) chloride, copper (II) bromide, Copper (II) acetate, copper (II) carbonate and the like are used, but copper (I) iodide and copper (I) oxide are preferably used, and copper (I) iodide is particularly preferably used. These copper compounds are used per mole of the compound of the general formula (I).
Preferably 0.01 to 10 mol, more preferably 0.0
5 to 1 mol are used. The reaction temperature is preferably from 100 to 150 ° C, particularly preferably from 120 to 140 ° C. The reaction time is 0.5-5 hours, preferably 1-3 hours.
【0029】以下に、一般式(I)で表わされる化合物
及び一般式(IV)で表わされる化合物の具体例を示す
が、本発明はこれらによって限定されるものではない。Hereinafter, specific examples of the compound represented by the general formula (I) and the compound represented by the general formula (IV) are shown, but the present invention is not limited thereto.
【0030】[0030]
【化16】 Embedded image
【0031】[0031]
【化17】 Embedded image
【0032】[0032]
【化18】 Embedded image
【0033】[0033]
【化19】 Embedded image
【0034】[0034]
【化20】 Embedded image
【0035】[0035]
【化21】 Embedded image
【0036】[0036]
【化22】 Embedded image
【0037】[0037]
【化23】 Embedded image
【0038】[0038]
【化24】 Embedded image
【0039】[0039]
【実施例】以下に本発明を実施例に基づき、さらに詳細
に説明する。 実施例1(一般式(I)の化合物(4)の合成) トルエン250ml、THF 100mlの混合溶媒中
に、水素化ナトリウム(60%)25.2gを加え、窒
素雰囲気下、加熱還流を行い、これに炭酸ジメチル3
7.5mlを加え、さらにγ−ブチロラクトン25.8
gを1時間かけて滴下した。滴下後、2時間加熱還流を
行い、ヨウ化エチル60mlをDMF40mlに溶かし
た溶液を15分かけて滴下した。滴下後1時間加熱還流
を行ったのち、室温にもどし、酢酸エチル500ml、
水500mlを加え、分液を行い、有機層を飽和食塩水
で洗い、硫酸マグネシウムで乾燥した。溶媒を留去後、
カラムクロマトグラフィーにて精製を行い、2−エチル
−2−メトキシカルボニルブタノリドを無色油状物とし
て27.6g(収率54%)得た。次いで、2−エチル
−2−メトキシカルボニルブタノリド34.4gをトル
エン500ml、THF 100mlに溶かし、これに
水素化ナトリウム(60%)17.6gを加え、窒素雰
囲気下、加熱還流を行い、これにアセトニトリル8.2
gを少量ずつ加えた。滴下後、酢酸10mlをトルエン
50mlで希釈し、少量ずつ滴下した。室温にもどし、
氷水に注ぎ、濃塩酸45mlにて酸性化したのち、酢酸
エチルで抽出した。カラムクロマトグラフィーにて精製
を行い、(4)を無色油状物として、19.8g(収率
55%)得た。The present invention will be described in more detail with reference to the following examples. Example 1 (Synthesis of compound (4) of general formula (I)) In a mixed solvent of 250 ml of toluene and 100 ml of THF, 25.2 g of sodium hydride (60%) was added, and the mixture was heated and refluxed under a nitrogen atmosphere. Dimethyl carbonate 3
7.5 ml were added, and γ-butyrolactone was 25.8.
g was added dropwise over 1 hour. After the dropwise addition, the mixture was heated under reflux for 2 hours, and a solution of 60 ml of ethyl iodide dissolved in 40 ml of DMF was added dropwise over 15 minutes. After heating and refluxing for 1 hour after the dropwise addition, the temperature was returned to room temperature, and 500 ml of ethyl acetate was added.
500 ml of water was added, liquid separation was performed, and the organic layer was washed with saturated saline and dried over magnesium sulfate. After distilling off the solvent,
Purification was performed by column chromatography to obtain 27.6 g (yield: 54%) of 2-ethyl-2-methoxycarbonylbutanolide as a colorless oil. Next, 34.4 g of 2-ethyl-2-methoxycarbonylbutanolide was dissolved in 500 ml of toluene and 100 ml of THF, and 17.6 g of sodium hydride (60%) was added thereto. The mixture was heated and refluxed under a nitrogen atmosphere. Acetonitrile 8.2
g was added in small portions. After the addition, 10 ml of acetic acid was diluted with 50 ml of toluene, and added dropwise little by little. Return to room temperature,
The mixture was poured into ice water, acidified with 45 ml of concentrated hydrochloric acid, and extracted with ethyl acetate. Purification was performed by column chromatography to obtain 19.8 g (55% yield) of (4) as a colorless oil.
【0040】mass:M+=181(base peak=57)IR (cm-1; neat/KBr) 2260, 2220, 1760, 1725, 1640, 1460, 1380, 1320, 12
20, 1200, 1180,1060, 1030, 1000, 960, 940, 900, 80
0, 730, 690 1H-NMR δppm(CDCL3 : 200MHz) 0.97(t, 3H, J=8.0Hz) 1.83-2.24(m, 3H) 2.92-3.07(m, 1H) 3.84(d, 1H, J=20.0Hz) 4.06(d, 1H, J=20.0Hz) 4.22-4.44(m, 2H) 他の一般式(I)の化合物も同様にして合成できる。 Mass : M + = 181 (base peak = 57) IR (cm −1 ; neat / KBr) 2260, 2220, 1760, 1725, 1640, 1460, 1380, 1320, 12
20, 1200, 1180, 1060, 1030, 1000, 960, 940, 900, 80
0, 730, 690 1 H-NMR δppm (CDCL 3 : 200MHz) 0.97 (t, 3H, J = 8.0Hz) 1.83-2.24 (m, 3H) 2.92-3.07 (m, 1H) 3.84 (d, 1H, J = 20.0Hz) 4.06 (d, 1H, J = 20.0Hz) 4.22-4.44 (m, 2H) Other compounds of the general formula (I) can be synthesized in the same manner.
【0041】実施例2(化合物(4)を用いた3−(1
−エチルシクロプロピル)−3−オキソ−プロパンニト
リル〔一般式(IV)、R1 =R2 =R3 =R4 =R6 =
R7 =H、R5 =C2 H5 〕の合成) 化合物(4)1.80g(0.01mol)にヨウ化リ
チウム0.40g(30mol%)を加え、これに2,
4,6−コリジン20mlを加え、窒素雰囲気下、油浴
温度150℃にて2時間加熱撹拌した。室温にもどし、
酢酸エチル200mlを加え、希塩酸水洗を繰り返し、
2,4,6−コリジンを除去した。次いで、水酸化ナト
リウム3%水溶液を加え、抽出分液を行い、水層を次い
で塩酸を用いて酸性化し、酢酸エチルを用いて抽出を行
った。硫酸マグネシウムにて乾燥後、溶媒を留去して、
3−(1−エチルシクロプロピル)−3−オキソ−プロ
パンニトリルを淡かっ色油状物として、0.82g(収
率60%)得た。Example 2 (3- (1) using compound (4)
-Ethylcyclopropyl) -3-oxo-propanenitrile [general formula (IV), R 1 = R 2 = R 3 = R 4 = R 6 =
Synthesis of R 7 = H, R 5 = C 2 H 5 ] 0.40 g (30 mol%) of lithium iodide was added to 1.80 g (0.01 mol) of compound (4), and 2,2
20 ml of 4,6-collidine was added, and the mixture was heated and stirred at an oil bath temperature of 150 ° C. for 2 hours under a nitrogen atmosphere. Return to room temperature,
200 ml of ethyl acetate was added, and washing with diluted hydrochloric acid was repeated.
2,4,6-collidine was removed. Next, a 3% aqueous solution of sodium hydroxide was added thereto to carry out extraction and separation. The aqueous layer was then acidified with hydrochloric acid, and extracted with ethyl acetate. After drying over magnesium sulfate, the solvent was distilled off,
0.82 g (60% yield) of 3- (1-ethylcyclopropyl) -3-oxo-propanenitrile was obtained as a pale brown oil.
【0042】mass:M+=137 1H-NMR (CDCL3 : 200MHz) δppm 0.92(dd, 2H, J=4.7, 6.6Hz) 0.99(t, 3H, J=7.6Hz) 1.26(dd, 2H, J=4.7, 6.6Hz) 1.69(q, 2H, J=7.6Hz) 3.48(s, 2H)The mass: M + = 137 1 H -NMR (CDCL 3: 200MHz) δppm 0.92 (dd, 2H, J = 4.7, 6.6Hz) 0.99 (t, 3H, J = 7.6Hz) 1.26 (dd, 2H, J = 4.7, 6.6Hz) 1.69 (q, 2H, J = 7.6Hz) 3.48 (s, 2H)
【0043】実施例3(3−(1−エチルシクロプロピ
ル)−3−オキソ−プロパンニトリルの合成) 化合物(4)1.80g(0.01mol)にヨウ化リ
チウム0.40g(30mol%)、ヨウ化銅(I)
0.57g(30mol%)、2,4,6−コリジン2
0mlを加え、油浴温度130℃にて4時間反応させ
た。実施例2と同様の処理を行い、3−(1−エチルシ
クロプロピル)−3−オキソ−プロパンニトリル0.8
5g(収率62%)得た。このように銅化合物を用いる
ことにより、前述の実施例2よりも20℃も反応温度が
低くても高収率で目的物を得ることができている(実施
例2では反応時間を4時間にしても特に収率の向上はみ
られなかった。)。Example 3 (Synthesis of 3- (1-ethylcyclopropyl) -3-oxo-propanenitrile) 0.40 g (30 mol%) of lithium iodide was added to 1.80 g (0.01 mol) of compound (4). Copper (I) iodide
0.57 g (30 mol%), 2,4,6-collidine 2
0 ml was added, and the mixture was reacted at an oil bath temperature of 130 ° C. for 4 hours. The same treatment as in Example 2 was carried out to give 3- (1-ethylcyclopropyl) -3-oxo-propanenitrile 0.8
5 g (yield 62%) was obtained. By using the copper compound in this manner, the target compound can be obtained in high yield even at a reaction temperature of 20 ° C. lower than that of Example 2 described above (in Example 2, the reaction time was set to 4 hours). However, no particular improvement in yield was observed.)
【0044】比較例1 化合物(4)1.80gにヨウ化ナトリウム0.40g
を加え、これにN−メチルピロリドン20mlを加え、
窒素雰囲気下、油浴温度150℃にて2時間加熱撹拌し
た。実施例2に比べ、反応が非常に遅く、化合物(4)
が残存した。実施例2を同様の後処理を行い、さらにカ
ラムクロマトグラフィーにて精製を行い、3−(1−エ
チルシクロプロピル)−3−オキソ−プロパンニトリル
を0.14g(収率10%)得た。Comparative Example 1 0.40 g of sodium iodide was added to 1.80 g of compound (4).
And 20 ml of N-methylpyrrolidone is added thereto.
Under a nitrogen atmosphere, the mixture was heated and stirred at an oil bath temperature of 150 ° C. for 2 hours. Compared with Example 2, the reaction was much slower and compound (4)
Remained. Example 2 was subjected to the same post-treatment, and further purified by column chromatography to obtain 0.14 g (yield 10%) of 3- (1-ethylcyclopropyl) -3-oxo-propanenitrile.
【0045】比較例2 化合物(4)1.80gにヨウ化銅0.57g、2,
4,6−コリジン20mlを加え、油浴温度130℃に
て4時間撹拌した。全く反応せず化合物(4)に残存す
るため、油浴温度を160℃に上げ、さらに2時間撹拌
したが、目的物3−(1−エチルシクロプロピル)−3
−オキソプロパン−ニトリルは得られなかった。Comparative Example 2 0.57 g of copper iodide was added to 1.80 g of compound (4).
20 ml of 4,6-collidine was added, and the mixture was stirred at an oil bath temperature of 130 ° C. for 4 hours. Since the compound (4) did not react at all and remained in the compound (4), the oil bath temperature was raised to 160 ° C., and the mixture was stirred for 2 hours.
-Oxopropane-nitrile was not obtained.
【0046】[0046]
【発明の効果】本発明方法によれば、安価で入手容易な
化合物から合成できる化合物を出発原料とし、カラー写
真用イエローカプラー、除草剤などの合成中間体として
有用であるシアノアシルシクロプロパン化合物を、短工
程で比較的温和な条件下好収率で得ることができる。ま
た、本発明の2−シアノアシル−4−ブタノリド化合物
は上記のシアノアシルシクロプロパン化合物の合成反応
の出発原料として好適に用いられる。According to the method of the present invention, a cyanoacylcyclopropane compound which is useful as a synthetic intermediate such as a yellow coupler for color photography or a herbicide is used as a starting material from a compound which can be synthesized from an inexpensive and easily available compound. In a short process and under relatively mild conditions in good yield. Further, the 2-cyanoacyl-4-butanolide compound of the present invention is suitably used as a starting material for the above-mentioned synthesis reaction of the cyanoacylcyclopropane compound.
───────────────────────────────────────────────────── フロントページの続き (58)調査した分野(Int.Cl.7,DB名) CA(STN) CAOLD(STN) REGISTRY(STN)──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. 7 , DB name) CA (STN) CAOLD (STN) REGISTRY (STN)
Claims (4)
それぞれ水素原子、アルキル基、アリール基、アルコキ
シ基、アリールオキシ基、アルキルチオ基又はアリール
チオ基を表わす。)で表わされる2−シアノアシル−4
−ブタノリド化合物をピリジン系溶媒を用い、アルカリ
金属ヨウ化物の存在下で脱炭酸環縮小反応させることを
特徴とする一般式(IV) 【化2】 (式中、R1 、R2 、R3 、R4 、R5 、R6 、R7 は
一般式(I)におけるものと同義である。)で表わされ
るシアノアシルシクロプロパン化合物の製造方法。1. A compound of the general formula (I) (Wherein, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 each represent a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, or an arylthio group. 2-cyanoacyl-4 represented by the formula:
A decarboxylation ring contraction reaction of a butanolide compound using a pyridine-based solvent in the presence of an alkali metal iodide; (Wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 have the same meanings as those in formula (I)).
におけるものと同義であり、R8 はアルキル基を表わ
す。)で表わされるγ−ブチロラクトン誘導体と、一般
式(III) 【化4】 (式中、R6 、R7 は一般式(I)におけるものと同義
である。)で表わされるアセトニトリル化合物を反応さ
せて一般式(I)で表わされる2−シアノアシル−4−
ブタノリド化合物を得ることを特徴とする請求項1記載
のシアノアシルシクロプロパン化合物の製造方法。2. A compound of the general formula (II) (Wherein R 1 , R 2 , R 3 , R 4 , and R 5 are those represented by the general formula (I)
And R 8 represents an alkyl group. Γ-butyrolactone derivative represented by the general formula (III): (Wherein R 6 and R 7 have the same meanings as in the general formula (I)), and are reacted with an acetonitrile compound represented by the general formula (I).
The method for producing a cyanoacylcyclopropane compound according to claim 1, wherein a butanolide compound is obtained.
2価の銅化合物を共存させて反応させることを特徴とす
る請求項1又は2記載のシアノアシルシクロプロパン化
合物の製造方法。3. The method for producing a cyanoacylcyclopropane compound according to claim 1, wherein the reaction is carried out in the coexistence of a monovalent or divalent copper compound in the decarboxylation ring reduction reaction.
それぞれ水素原子、アルキル基、アリール基、アルコキ
シ基、アリールオキシ基、アルキルチオ基又はアリール
チオ基を表わす。)で表わされる2−シアノアシル−4
−ブタノリド化合物。4. A compound of the general formula (I) (Wherein, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 each represent a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, or an arylthio group. 2-cyanoacyl-4 represented by the formula:
-Butanolide compounds.
Priority Applications (1)
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JP23545893A JP3241889B2 (en) | 1993-08-27 | 1993-08-27 | Method for producing cyanoacylcyclopropane compound and 2-cyanoacyl-4-butanolide compound used therefor |
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---|---|---|---|
JP23545893A JP3241889B2 (en) | 1993-08-27 | 1993-08-27 | Method for producing cyanoacylcyclopropane compound and 2-cyanoacyl-4-butanolide compound used therefor |
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JPH0770037A JPH0770037A (en) | 1995-03-14 |
JP3241889B2 true JP3241889B2 (en) | 2001-12-25 |
Family
ID=16986404
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CN107848995B (en) * | 2015-04-14 | 2021-12-28 | 杜邦公司 | Process for producing 2, 5-furandicarboxylic acid and derivatives thereof and polymers made therefrom |
US10582709B2 (en) | 2015-04-27 | 2020-03-10 | Fmc Corporation | Butyrolactones as herbicides |
WO2017023515A1 (en) | 2015-07-31 | 2017-02-09 | E. I. Du Pont De Nemours And Company | Cyclic n-carboxamide compounds useful as herbicides |
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CN110691516B (en) | 2017-03-21 | 2022-10-28 | Fmc公司 | Pyrrolidone and preparation method thereof |
CN109608317B (en) * | 2018-12-26 | 2021-11-12 | 瑞孚信江苏药业股份有限公司 | Synthetic method for preparing cyclopropyl methyl ketone by cracking alpha-acetyl-gamma-butyrolactone |
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