CN1176917C - 生产吡喃酮化合物的方法 - Google Patents
生产吡喃酮化合物的方法Info
- Publication number
- CN1176917C CN1176917C CNB011410531A CN01141053A CN1176917C CN 1176917 C CN1176917 C CN 1176917C CN B011410531 A CNB011410531 A CN B011410531A CN 01141053 A CN01141053 A CN 01141053A CN 1176917 C CN1176917 C CN 1176917C
- Authority
- CN
- China
- Prior art keywords
- methyl
- carbonate
- pyrans
- alkaline earth
- hydroxide
- Prior art date
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- -1 pyrone compound Chemical class 0.000 title claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 11
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims description 24
- 150000001875 compounds Chemical class 0.000 claims description 12
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 9
- 235000010755 mineral Nutrition 0.000 claims description 9
- 239000011707 mineral Substances 0.000 claims description 9
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Chemical compound [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 claims description 8
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 7
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical group [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 3
- 235000015320 potassium carbonate Nutrition 0.000 claims description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 2
- 239000000920 calcium hydroxide Substances 0.000 claims description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 2
- 235000012204 lemonade/lime carbonate Nutrition 0.000 claims description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical group [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 2
- 239000001095 magnesium carbonate Substances 0.000 claims description 2
- 235000014380 magnesium carbonate Nutrition 0.000 claims description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical group [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 2
- 229960001708 magnesium carbonate Drugs 0.000 claims description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 2
- 239000000347 magnesium hydroxide Substances 0.000 claims description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 125000005594 diketone group Chemical group 0.000 claims 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 10
- 239000003513 alkali Substances 0.000 abstract 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 abstract 2
- RJJHLSTYKMSPHP-UHFFFAOYSA-N 4-hydroxy-6-methyl-3-(4-methylpent-2-enoyl)pyran-2-one Chemical compound CC(C)C=CC(=O)C1=C(O)C=C(C)OC1=O RJJHLSTYKMSPHP-UHFFFAOYSA-N 0.000 abstract 1
- HNTJUUUAXYDMTE-UHFFFAOYSA-N 7-methyl-2-propan-2-yl-2,3-dihydropyrano[4,3-b]pyran-4,5-dione Chemical compound C1=C(C)OC(=O)C2=C1OC(C(C)C)CC2=O HNTJUUUAXYDMTE-UHFFFAOYSA-N 0.000 abstract 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 abstract 1
- 150000002222 fluorine compounds Chemical class 0.000 abstract 1
- 150000004679 hydroxides Chemical class 0.000 abstract 1
- 150000002484 inorganic compounds Chemical class 0.000 abstract 1
- 229910010272 inorganic material Inorganic materials 0.000 abstract 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- 238000004519 manufacturing process Methods 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- 239000011541 reaction mixture Substances 0.000 description 7
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 239000012044 organic layer Substances 0.000 description 6
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- AJFJTORMMHWKFW-UHFFFAOYSA-N Dhelwangin Chemical compound CC(C)CCC(=O)C1=C(O)C=C(C)OC1=O AJFJTORMMHWKFW-UHFFFAOYSA-N 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 229910001512 metal fluoride Inorganic materials 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 241000257159 Musca domestica Species 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000004480 active ingredient Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 239000004287 Dehydroacetic acid Substances 0.000 description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- AMIMRNSIRUDHCM-UHFFFAOYSA-N Isopropylaldehyde Chemical compound CC(C)C=O AMIMRNSIRUDHCM-UHFFFAOYSA-N 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- JEQRBTDTEKWZBW-UHFFFAOYSA-N dehydroacetic acid Chemical compound CC(=O)C1=C(O)OC(C)=CC1=O JEQRBTDTEKWZBW-UHFFFAOYSA-N 0.000 description 2
- 229940061632 dehydroacetic acid Drugs 0.000 description 2
- PGRHXDWITVMQBC-UHFFFAOYSA-N dehydroacetic acid Natural products CC(=O)C1C(=O)OC(C)=CC1=O PGRHXDWITVMQBC-UHFFFAOYSA-N 0.000 description 2
- 235000019258 dehydroacetic acid Nutrition 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229940043265 methyl isobutyl ketone Drugs 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- ZPSJGADGUYYRKE-UHFFFAOYSA-N 2H-pyran-2-one Chemical compound O=C1C=CC=CO1 ZPSJGADGUYYRKE-UHFFFAOYSA-N 0.000 description 1
- XENVBNVBWYWVMC-UHFFFAOYSA-N 3-(4-methylpentanoyl)pyran-2-one Chemical compound CC(CCC(=O)C=1C(OC=CC=1)=O)C XENVBNVBWYWVMC-UHFFFAOYSA-N 0.000 description 1
- 241001185697 Fenestella Species 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- 241000257226 Muscidae Species 0.000 description 1
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- PQVSTLUFSYVLTO-UHFFFAOYSA-N ethyl n-ethoxycarbonylcarbamate Chemical compound CCOC(=O)NC(=O)OCC PQVSTLUFSYVLTO-UHFFFAOYSA-N 0.000 description 1
- 150000002196 fatty nitriles Chemical class 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 150000005826 halohydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 230000000749 insecticidal effect Effects 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium hydroxide monohydrate Substances [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 description 1
- 229940040692 lithium hydroxide monohydrate Drugs 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
- C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
- C07D493/04—Ortho-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
- C07D309/34—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
- C07D309/36—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with oxygen atoms directly attached to ring carbon atoms
- C07D309/38—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with oxygen atoms directly attached to ring carbon atoms one oxygen atom in position 2 or 4, e.g. pyrones
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Pyrane Compounds (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
通过2，3-二氢-7-甲基-2-(1-甲基乙基)-4H，5H-吡喃并[4，3-b]吡喃-4，5-二酮与至少1种选自碱金属氢氧化物、碱土金属氢氧化物、碱金属碳酸盐、碱土金属碳酸盐和碱金属氟化物的无机化合物，在醇、水或二者的混合物中起反应制取4-羟基-6-甲基-3-(4-甲基-2-戊烯酰)-2-吡喃酮。
Description
技术领域
本发明涉及生产4-羟基-6-甲基-3-(4-甲基-2-戊烯酰(pentenoyl))-2-吡喃酮的方法。更具体地说，它涉及由2，3-二氢-7-甲基-2-(1-甲基乙基)-4H，5H-吡喃并(pyrano)[4，3-b]吡喃-4，5-二酮生产4-羟基-6-甲基-3-(4-甲基-2-戊烯酰)-2-吡喃酮的方法。
背景技术
通式(1)的4-羟基-6-甲基-3-(4-甲基-2-戊酰)吡喃酮：
是一种可用作杀虫剂的有效成分的化合物，它可由通式(2)的4-羟基-6-甲基-3-(4-甲基-2-戊烯酰)-2-吡喃酮的催化还原来制取：
因此，提供一种生产通式(2)化合物的方法是有用的。
本发明的目的是提供一种生产4-羟基-6-甲基-3-(4-甲基-2-戊烯酰)-2-吡喃酮的方法，该化合物是制造4-羟基-6-甲基-3-(4-甲基戊酰)-2-吡喃酮的中间体。
发明概述
本发明提供一种由通式(3)的2，3-二氢-7-甲基-2-(1-甲基乙基)-4H，5H-吡喃并[4，3-b]吡喃-4，5-二酮：
在特定条件下生产通式(2)的4-羟基-6-甲基-3-(4-甲基-2-戊烯酰)-2-吡喃酮的方法。式(2)的4-羟基-6-甲基-3-(4-甲基-2-戊烯酰)-2-吡喃酮通过催化还原程序可衍生为杀虫有效成分4-羟基-6-甲基-3-(4-甲基戊酰)-2-吡喃酮。
就是说，本发明提供一种生产4-羟基-6-甲基-3-(4-甲基-2-戊烯酰)-2-吡喃酮的方法，它包含让2，3-二氢-7-甲基-2-(1-甲基乙基)-4H，5H-吡喃并[4，3-b]吡喃-4，5-二酮与至少1种选自碱金属氢氧化物、碱土金属氢氧化物、碱金属碳酸盐、碱土金属碳酸盐和碱金属氟化物的无机化合物，在醇、水或二者的混合物中起反应。
发明详述
本发明方法是在醇、水或二者的混合物中进行的。
用于反应的醇的例子包括低级醇，例如C1～C5醇。典型例子是甲醇、乙醇、2-丙醇和2-甲基-2-丙醇。低级醇与水的混合物，乃至2或更多种低级醇的混合物均可使用。
在本发明中，对本发明反应呈惰性的其他溶剂也可一起使用。因此，术语“在醇、水或二者的混合物中”是指“在至少1种选自醇和水的溶剂存在下，并且溶剂的用量足以溶解选自碱金属氢氧化物、碱土金属氢氧化物、碱金属碳酸盐、碱土金属碳酸盐和碱金属氟化物的无机化合物。”选自醇和水的溶剂用量，一般为1mL～1000mL每克2，3-二氢-7-甲基-2-(1-甲基乙基)-4H，5H-吡喃并[4，3-b]吡喃-4，5-二酮。
惰性溶剂的例子包括脂族烃(例如，己烷)、芳烃(例如，甲苯)、酮(例如，甲基异丁基酮)、酯(例如，乙酸乙酯)、醚(例如，四氢呋喃、二乙醚)、酰胺(例如，N，N-二甲基甲酰胺)、卤代烃(例如，氯仿)、二甲基亚砜、脂族腈(例如，乙腈)、叔胺(例如，三乙胺)以及含氮芳族杂环(例如，吡啶)。
碱金属氢氧化物的例子包括氢氧化锂、氢氧化钠和氢氧化钾；碱土金属氢氧化物的例子包括氢氧化镁、氢氧化钙和氢氧化钡。在本发明中，碱金属碳酸盐是指碱金属碳酸盐的正盐。因此，碱金属碳酸盐的例子包括碳酸锂、碳酸钠和碳酸钾。碱土金属碳酸盐的例子包括碳酸镁、碳酸钙和碳酸钡。碱金属氟化物的例子包括氟化铯。
碱金属氢氧化物、碱土金属氢氧化物、碱金属碳酸盐、碱土金属碳酸盐或碱金属氟化物在反应中的用量一般介于1～10mol，优选1～5mol对1mol原料2，3-二氢-7-甲基-2-(1-甲基乙基)-4H，5H-吡喃并[4，3-b]吡喃-4，5-二酮。
本发明方法的反应温度一般介于-20～100℃，条件是，当反应使用的溶剂的沸点低于100℃时，反应通常是在一种溶剂的沸点下。反应时间随其他反应条件变化，它一般地介于从瞬间到24h。
本发明方法使用的原料2，3-二氢-7-甲基-2-(1-甲基乙基)-4H，5H-吡喃并[4，3-b]吡喃-4，5-二酮的制备可按照《化学与工业》，pp.1306～1307(1969)的描述，由脱氢乙酸与异丁醛在哌啶-氯仿溶液存在下的缩合反应来实现。
另外，按本发明方法获得的4-羟基-6-甲基-3-(4-甲基-2-戊烯酰)-2-吡喃酮可进行还原，例如在过渡金属催化剂存在下进行氢化，从而获得4-羟基-6-甲基-3-(4-甲基戊酰)-2-吡喃酮作为杀虫剂的活性成份。
实施例
下面将通过生产实例等详细进一步说明本发明，尽管本发明从任何意义上均不限于这些实施例。
生产实例1
在10mL甲醇中，溶解进222mg 2，3-二氢-7-甲基-2-(1-甲基乙基)-4H，5H-吡喃并[4，3-b]吡喃-4，5-二酮，向其中加入200mg氢氧化钾，然后在室温下搅拌1h。此后，向反应混合物中加入甲基叔丁基醚和3％盐酸。用饱和盐水洗涤分离的有机层一次，经无水硫酸镁干燥并在减压下浓缩，从而获得130mg 4-羟基-6-甲基-3-(4-甲基-2-戊烯酰)-2-吡喃酮。
1H-NMR(CDCl3，TMS)δ(ppm)：1.13(6H，d)，2.27(3H，s)，2.60(1H，m)，5.93(1H，s)，7.23(1H，dd)，7.58(1H，d)
生产实例2
向450mg 2，3-二氢-7-甲基-2-(1-甲基乙基)-4H，5H-吡喃并[4，3-b]吡喃-4，5-二酮与40mL2-丙醇的混合物中，加入400mg碳酸钾并在室温下搅拌12h。随后，反应混合物进行浓缩，向其中加入甲基叔丁基醚和3％盐酸。用饱和盐水洗涤分离的有机层一次，经无水硫酸镁干燥并在减压下浓缩，从而获得340mg 4-羟基-6-甲基-3-(4-甲基-2-戊烯酰)-2-吡喃酮。
生产实例3
向200mg 2，3-二氢-7-甲基-2-(1-甲基乙基)-4H，5H-吡喃并[4，3-b]吡喃-4，5-二酮与10mL水的混合物中，加入200mg氢氧化锂一水合物并在室温下搅拌1h。随后，向反应混合物中加入甲基叔丁基醚和3％盐酸。用饱和盐水洗涤分离的有机层一次，经无水硫酸镁干燥并在减压下浓缩，从而获得178mg 4-羟基-6-甲基-3-(4-甲基-2-戊烯酰)-2-吡喃酮。
生产实例4
108mg 2，3-二氢-7-甲基-2-(1-甲基乙基)-4H，5H-吡喃并[4，3-b]吡喃-4，5-二酮、200mg氟化铯以及5mL 2-甲基-2-丙醇的混合物，在回流加热下搅拌2h。随后，向反应混合物中加入甲基叔丁基醚和3％盐酸。用饱和盐水洗涤分离的有机层一次，经无水硫酸镁干燥并在减压下浓缩，从而获得86mg 4-羟基-6-甲基-3-(4-甲基-2-戊烯酰)-2-吡喃酮。
生产实例5
向189mg 2，3-二氢-7-甲基-2-(1-甲基乙基)-4H，5H-吡喃并[4，3-b]吡喃-4，5-二酮、4mL甲苯以及4mL水的混合物中，加入0.20g氢氧化钠并搅拌。4h后，向反应混合物中加入甲基叔丁基醚和3％盐酸。用饱和盐水洗涤分离的有机层一次，经无水硫酸镁干燥并在减压下浓缩，从而获得82mg 4-羟基-6-甲基-3-(4-甲基-2-戊烯酰)-2-吡喃酮。
下面，用参考生产实例举例说明通过4-羟基-6-甲基-3-(4-甲基-2-戊烯酰)-2-吡喃酮的还原生产4-羟基-6-甲基-3-(4-甲基戊酰)-2-吡喃酮的方法。
参比生产实例
在氮气氛下，2.8g 4-羟基-6-甲基-3-(4-甲基-2-戊烯酰)-2-吡喃酮溶解在乙酸乙酯中，并向其中加入0.14g 5％钯/炭。用氢气置换反应容器中的氮气，随后反应混合物在室温下搅拌5h。此后，反应混合物经硅藻土垫过滤，用50mL乙酸乙酯洗涤硅藻土垫。滤液与洗涤溶液合并的溶液，依次用0.1％盐酸洗涤1次，水洗2次，然后饱和盐水洗涤1次。有机层用无水硫酸镁水干燥并在减压下浓缩，结果获得残渣，该残渣用硅胶柱色谱术处理(洗脱液：己烷/乙酸乙酯＝6/1)，结果获得2.68g 4-羟基-6-甲基-3-(4-甲基戊酰)-2-吡喃酮。
1H-NMR(CDCl3，TMS)δ(ppm)：0.94(6H，d)，1.54(2H，q)，1.63(1H，m)，2.27(3H，s)，3.08(2H，t)，5.93(1H，s)，17.88(1H，s)
进而，将通过参考实例展示，上面获得的4-羟基-6-甲基-3-(4-甲基戊酰)-2-吡喃酮可以用作杀虫剂有效成分。
参考实例(针对家蝇的击落试验)
半份4-羟基-6-甲基-3-(4-甲基戊酰)-2-吡喃酮，溶解在10份二氯甲烷中并与89.5份IsoparM(埃克森化学公司生产的异链烷烃)混合，制备成0.5％油溶液。份数是指重量份。
10只成年家蝇(Musca domestica)，包括5只雄性和5只雌性，放入到70cm3玻璃室(容积：0.34cm3)。采用喷雾枪，在0.9kg/cm2的压力下经玻璃室壁的小窗喷入0.7mL上述油溶液。喷入后15min，观察击落的家蝇数目。根据2次重复试验的结果，击落比例是95％。
Claims (12)
1.一种生产4-羟基-6-甲基-3-(4-甲基-2-戊烯酰)-2-吡喃酮的方法，它包含让2，3-二氢-7-甲基-2-(1-甲基乙基)-4H，5H-吡喃并[4，3-b]吡喃-4，5-二酮与至少1种选自碱金属氢氧化物、碱土金属氢氧化物、碱金属碳酸盐、碱土金属碳酸盐和氟化铯的无机化合物，在C1-C5醇、水或二者的混合物中，在反应温度介于-20到100℃，摩尔比为1-10摩尔所述无机化合物对1摩尔2，3-二氢-7-甲基-2-(1-甲基乙基)-4H，5H-吡喃并[4，3-b]吡喃-4，5-二酮时起反应。
2.权利要求1的方法，其中反应在C1-C5醇中进行。
3.权利要求1的方法，其中反应在水中进行。
4.权利要求1的方法，其中无机化合物是碱金属氢氧化物。
5.权利要求4的方法，其中碱金属氢氧化物是氢氧化锂、氢氧化钠或氢氧化钾。
6.权利要求1的方法，其中无机化合物是碱土金属氢氧化物。
7.权利要求6的方法，其中碱土金属氢氧化物是氢氧化镁、氢氧化钙或氢氧化钡。
8.权利要求1的方法，其中无机化合物是碱金属碳酸盐。
9.权利要求8的方法，其中碱金属碳酸盐是碳酸锂、碳酸钠或碳酸钾。
10.权利要求1的方法，其中无机化合物是碱土金属碳酸盐。
11.权利要求10的方法，其中碱土金属碳酸盐是碳酸镁、碳酸钙或碳酸钡。
12.权利要求1的方法，其中无机化合物是氟化铯。
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| EP1193263B1 (en) | 2003-09-03 |
| HUP0103907A3 (en) | 2002-09-30 |
| KR20020025724A (ko) | 2002-04-04 |
| DE60100693D1 (de) | 2003-10-09 |
| US6420569B1 (en) | 2002-07-16 |
| CN1344714A (zh) | 2002-04-17 |
| DE60100693T2 (de) | 2004-07-15 |
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| HU0103907D0 (en) | 2001-11-28 |
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