CN111533715B - 2(5h)-呋喃-2-酮衍生物及其制备方法以及在抑制水稻分蘖的应用 - Google Patents
2(5h)-呋喃-2-酮衍生物及其制备方法以及在抑制水稻分蘖的应用 Download PDFInfo
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- CN111533715B CN111533715B CN202010322187.2A CN202010322187A CN111533715B CN 111533715 B CN111533715 B CN 111533715B CN 202010322187 A CN202010322187 A CN 202010322187A CN 111533715 B CN111533715 B CN 111533715B
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- 125000006276 2-bromophenyl group Chemical group [H]C1=C([H])C(Br)=C(*)C([H])=C1[H] 0.000 description 1
- CJNZAXGUTKBIHP-UHFFFAOYSA-N 2-iodobenzoic acid Chemical compound OC(=O)C1=CC=CC=C1I CJNZAXGUTKBIHP-UHFFFAOYSA-N 0.000 description 1
- 125000006304 2-iodophenyl group Chemical group [H]C1=C([H])C(I)=C(*)C([H])=C1[H] 0.000 description 1
- ILYSAKHOYBPSPC-UHFFFAOYSA-N 2-phenylbenzoic acid Chemical compound OC(=O)C1=CC=CC=C1C1=CC=CC=C1 ILYSAKHOYBPSPC-UHFFFAOYSA-N 0.000 description 1
- KSNKQSPJFRQSEI-UHFFFAOYSA-N 3,3,3-trifluoropropanoic acid Chemical compound OC(=O)CC(F)(F)F KSNKQSPJFRQSEI-UHFFFAOYSA-N 0.000 description 1
- QBWKPGNFQQJGFY-QLFBSQMISA-N 3-[(1r)-1-[(2r,6s)-2,6-dimethylmorpholin-4-yl]ethyl]-n-[6-methyl-3-(1h-pyrazol-4-yl)imidazo[1,2-a]pyrazin-8-yl]-1,2-thiazol-5-amine Chemical compound N1([C@H](C)C2=NSC(NC=3C4=NC=C(N4C=C(C)N=3)C3=CNN=C3)=C2)C[C@H](C)O[C@H](C)C1 QBWKPGNFQQJGFY-QLFBSQMISA-N 0.000 description 1
- BAYGVMXZJBFEMB-UHFFFAOYSA-N 4-(trifluoromethyl)phenol Chemical compound OC1=CC=C(C(F)(F)F)C=C1 BAYGVMXZJBFEMB-UHFFFAOYSA-N 0.000 description 1
- ZOMMEPFDNFYOHO-UHFFFAOYSA-N 4-(trimethylsilyl)phenol Chemical compound C[Si](C)(C)C1=CC=C(O)C=C1 ZOMMEPFDNFYOHO-UHFFFAOYSA-N 0.000 description 1
- 125000004860 4-ethylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])C([H])([H])[H] 0.000 description 1
- ZGWGSEUMABQEMD-UHFFFAOYSA-N 4-methyl-1,3-thiazole-5-carboxylic acid Chemical compound CC=1N=CSC=1C(O)=O ZGWGSEUMABQEMD-UHFFFAOYSA-N 0.000 description 1
- 125000004399 C1-C4 alkenyl group Chemical group 0.000 description 1
- WBYWAXJHAXSJNI-SREVYHEPSA-N Cinnamic acid Chemical compound OC(=O)\C=C/C1=CC=CC=C1 WBYWAXJHAXSJNI-SREVYHEPSA-N 0.000 description 1
- 241000336315 Cistanche salsa Species 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- 241000238631 Hexapoda Species 0.000 description 1
- OPFJDXRVMFKJJO-ZHHKINOHSA-N N-{[3-(2-benzamido-4-methyl-1,3-thiazol-5-yl)-pyrazol-5-yl]carbonyl}-G-dR-G-dD-dD-dD-NH2 Chemical compound S1C(C=2NN=C(C=2)C(=O)NCC(=O)N[C@H](CCCN=C(N)N)C(=O)NCC(=O)N[C@H](CC(O)=O)C(=O)N[C@H](CC(O)=O)C(=O)N[C@H](CC(O)=O)C(N)=O)=C(C)N=C1NC(=O)C1=CC=CC=C1 OPFJDXRVMFKJJO-ZHHKINOHSA-N 0.000 description 1
- QXJXTQWYEGJQLU-UHFFFAOYSA-N O=C(CC(F)(F)F)OC(C=C1)OC1=O Chemical compound O=C(CC(F)(F)F)OC(C=C1)OC1=O QXJXTQWYEGJQLU-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000000692 Student's t-test Methods 0.000 description 1
- 241000607479 Yersinia pestis Species 0.000 description 1
- LJOOWESTVASNOG-UFJKPHDISA-N [(1s,3r,4ar,7s,8s,8as)-3-hydroxy-8-[2-[(4r)-4-hydroxy-6-oxooxan-2-yl]ethyl]-7-methyl-1,2,3,4,4a,7,8,8a-octahydronaphthalen-1-yl] (2s)-2-methylbutanoate Chemical compound C([C@H]1[C@@H](C)C=C[C@H]2C[C@@H](O)C[C@@H]([C@H]12)OC(=O)[C@@H](C)CC)CC1C[C@@H](O)CC(=O)O1 LJOOWESTVASNOG-UFJKPHDISA-N 0.000 description 1
- 238000012271 agricultural production Methods 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- XRWSZZJLZRKHHD-WVWIJVSJSA-N asunaprevir Chemical compound O=C([C@@H]1C[C@H](CN1C(=O)[C@@H](NC(=O)OC(C)(C)C)C(C)(C)C)OC1=NC=C(C2=CC=C(Cl)C=C21)OC)N[C@]1(C(=O)NS(=O)(=O)C2CC2)C[C@H]1C=C XRWSZZJLZRKHHD-WVWIJVSJSA-N 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- KGNDCEVUMONOKF-UGPLYTSKSA-N benzyl n-[(2r)-1-[(2s,4r)-2-[[(2s)-6-amino-1-(1,3-benzoxazol-2-yl)-1,1-dihydroxyhexan-2-yl]carbamoyl]-4-[(4-methylphenyl)methoxy]pyrrolidin-1-yl]-1-oxo-4-phenylbutan-2-yl]carbamate Chemical compound C1=CC(C)=CC=C1CO[C@H]1CN(C(=O)[C@@H](CCC=2C=CC=CC=2)NC(=O)OCC=2C=CC=CC=2)[C@H](C(=O)N[C@@H](CCCCN)C(O)(O)C=2OC3=CC=CC=C3N=2)C1 KGNDCEVUMONOKF-UGPLYTSKSA-N 0.000 description 1
- 230000008827 biological function Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229930016911 cinnamic acid Natural products 0.000 description 1
- 235000013985 cinnamic acid Nutrition 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 229940125810 compound 20 Drugs 0.000 description 1
- 229940126086 compound 21 Drugs 0.000 description 1
- 229940126208 compound 22 Drugs 0.000 description 1
- 229940125833 compound 23 Drugs 0.000 description 1
- 229940125961 compound 24 Drugs 0.000 description 1
- 229940125846 compound 25 Drugs 0.000 description 1
- 229940125851 compound 27 Drugs 0.000 description 1
- 229940125898 compound 5 Drugs 0.000 description 1
- VZFUCHSFHOYXIS-UHFFFAOYSA-N cycloheptane carboxylic acid Natural products OC(=O)C1CCCCCC1 VZFUCHSFHOYXIS-UHFFFAOYSA-N 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- GOUILHYTHSOMQJ-UHFFFAOYSA-N gamma-butenolide Natural products CCC1OC(=O)C=C1 GOUILHYTHSOMQJ-UHFFFAOYSA-N 0.000 description 1
- 239000001963 growth medium Substances 0.000 description 1
- JAXFJECJQZDFJS-XHEPKHHKSA-N gtpl8555 Chemical compound OC(=O)C[C@H](N)C(=O)N[C@@H](CCC(O)=O)C(=O)N[C@@H](C(C)C)C(=O)N[C@@H](C(C)C)C(=O)N1CCC[C@@H]1C(=O)N[C@H](B1O[C@@]2(C)[C@H]3C[C@H](C3(C)C)C[C@H]2O1)CCC1=CC=C(F)C=C1 JAXFJECJQZDFJS-XHEPKHHKSA-N 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- ZLVXBBHTMQJRSX-VMGNSXQWSA-N jdtic Chemical compound C1([C@]2(C)CCN(C[C@@H]2C)C[C@H](C(C)C)NC(=O)[C@@H]2NCC3=CC(O)=CC=C3C2)=CC=CC(O)=C1 ZLVXBBHTMQJRSX-VMGNSXQWSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 1
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 1
- 229950010765 pivalate Drugs 0.000 description 1
- IUGYQRQAERSCNH-UHFFFAOYSA-N pivalic acid Chemical compound CC(C)(C)C(O)=O IUGYQRQAERSCNH-UHFFFAOYSA-N 0.000 description 1
- 239000003375 plant hormone Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000007226 seed germination Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000007039 two-step reaction Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/60—Two oxygen atoms, e.g. succinic anhydride
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
- A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
- A01N43/06—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings
- A01N43/08—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings with oxygen as the ring hetero atom
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
- A01N43/36—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom five-membered rings
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
- A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
- A01N43/78—1,3-Thiazoles; Hydrogenated 1,3-thiazoles
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N55/00—Biocides, pest repellants or attractants, or plant growth regulators, containing organic compounds containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen and sulfur
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
- C07D405/12—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a chain containing hetero atoms as chain links
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- C07D417/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
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Abstract
本发明公开了如式Ⅰ所示的2(5H)‑呋喃‑2‑酮衍生物，R为如式
所示的取代或未取代的苯基、取代或未取代的萘基、
本发明还公开了2(5H)‑呋喃‑2‑酮衍生物的制备方法：以ROH和5‑溴‑呋喃‑2(5H)‑酮为原料，以水和有机溶剂为反应溶剂，在无机碱和相转移催化剂存在的条件下反应得到目标化合物。本发明2(5H)‑呋喃‑2‑酮衍生物具有抑制水稻分蘖的效果，相较于独脚金内酯GR24，2(5H)‑呋喃‑2‑酮衍生物结构简单、制备价格低廉，成本不到GR24商品化价格的万分之一，对于水稻分蘖的应用具有潜在的商业化前景。
Description
技术领域
本发明涉及一类2(5H)-呋喃-2-酮衍生物及其制备方法以及在抑制水稻分蘖的应用。
背景技术
独脚金内酯(strigolactone,SL)是一类植物激素化合物，具有诱导独脚金属和列当属植物种子萌发、促进丛枝菌根真菌的菌丝分枝、抑制植物分枝的形成和介导植物逆境胁迫的抗性反应等生物学功能而备受关注，特别是能够抑制水稻产生过多的分蘖，有利于培育优质理想植株，因此有望通过控制无效分蘖从而提升水稻产量。
由于植物中SL含量极低(在水稻根中独脚金内酯的检出限是20ng/kg)，难以通过分离提取的方式得到，另外其全合成的难度大、总产率低，因此科学家通过人工合成GR系列衍生物等类似物实现替代，当中又以GR24的生物活性最高，应用范围最为广泛。尽管GR24的全合成报道可追溯到上世纪九十年代(J.Agric.Food Chem.1992,40,1230)，然而其合成路线冗长难以实现工业化生产。目前商品化的GR24价格非常昂贵，每100毫克高达数万元人民币(荷兰Chiralix公司报价)。如此昂贵的价格使得独脚金内酯在农业生产中的应用变得遥不可及，因此发展易生产、价格低廉的新型控蘖化合物成为生产上的迫切要求。目前尚未有廉价且易合成的独脚金内酯类似物的报道或专利。
发明内容
发明人通过研究表明2(5H)-呋喃-2-酮结构(又称为γ-丁烯内酯)是独脚金内酯系列化合物的核心单元，发明人通过两步反应获得2(5H)-呋喃-2-酮衍生物，该类化合物在保持抑制水稻分蘖生物活性的同时，其化学结构被大大简化，制备成本低廉，成本不到GR24商品化价格的万分之一，一定程度上有利于加速其商业化的进程。
本发明的目的是通过以下技术方案实现的：
一种如式Ⅰ所示的2(5H)-呋喃-2-酮衍生物：
其中，R为如式
所示的取代或未取代的苯基、取代或未取代的萘基、
n＝0～5的整数，R1选自卤素、C1-C4烷基、卤素取代的C1-C4烷基、C1-C4烷氧基、卤素取代的C1-C4烷氧基、-SiR4R5R6(硅烷基)、-N+R7R8R9X-；R4、R5、R6分别独立的选自C1-C3烷基，R7、R8、R9分别独立的选自C1-C3烷基，X-选自卤素阴离子；
萘基的取代基为卤素、C1-C4烷基、卤素取代的C1-C4烷基、C1-C4烷氧基、卤素取代的C1-C4烷氧基；
m＝0～5的整数，R2选自O或共价键，R3选自C1-C4烷基、卤素取代的C1-C4烷基、C5-C6环烷基、取代或未取代的C1-C4烯基、取代或未取代的苯基、取代或未取代的萘基、取代或未取代的含有N和/或S的5-6元不饱和杂环基团。
优选的，R为如式
所示的取代的苯基、1-萘基、1-溴-2-萘基、
n＝1～3的整数，R1选自F、Cl、Br、C1-C2烷基、卤素取代的C1-C2烷基、C1-C2烷氧基、三甲基硅烷基、N,N,N-三甲基碘代季铵盐(-N+(CH3)3I-)；
m＝0或1，R2选自O或共价键，R3选自卤素取代的甲基、C3-C4直链或支链烷基、C5-C6环烷基、苯乙烯基、卤素或苯基取代的苯基、1-萘基、4-甲基-5-噻唑基、N-BOC-吡咯基
进一步优选的，R为如式
所示的取代的苯基、
n＝1～3的整数，R1选自F、Cl、Br、C1-C2烷基、卤素取代的C1-C2烷基、C1-C2烷氧基、三甲基硅烷基、N,N,N-三甲基碘代季铵盐，但不包括2,6-二溴-4-甲基苯基、3-甲氧基苯基；
m＝0或1，R2选自O或共价键，R3选自卤素取代的苯基(具体选自2,4-二氟苯基、2-碘苯基、2,6-二氯苯基)、1-萘基、4-甲基-5-噻唑基。
n＝0时，
为未取代的苯基；n≠0时，
为取代的苯基。
所述的卤素为F、Cl、Br、I。
具体的，所述的2(5H)-呋喃-2-酮衍生物选自以下化合物：
5-(2,4-二氯苯氧基)呋喃-2(5H)-酮；5-(2,6-二氯苯氧基)呋喃-2(5H)-酮；5-(2-溴苯氧基)呋喃-2(5H)-酮；5-氧代-2,5-二氢呋喃-2-基-2-(2,4-二氟苯氧基)乙酸酯；5-氧代2,5-二氢呋喃-2-基3,3,3-三氟丙酸酯；5-(1-萘氧基)呋喃-2(5H)-酮；5-(1-溴-2-萘氧基)呋喃-2(5H)-酮；5-(2,6-二溴-4-甲基苯氧基)呋喃-2(5H)-酮；5-氧代-2,5-二氢呋喃-4-甲基噻唑-5-甲酸酯；5-氧代-2,5-二氢呋喃-2-基2-(2-苯基)苯甲酸酯；5-氧代2,5-二氢呋喃-2-基新戊酸酯；5-(4-乙基苯氧基)呋喃-2(5H)-酮；5-(3-甲氧基苯氧基)呋喃-2(5H)-酮；5-(2,4,6-三甲苯氧基)呋喃-2(5H)-酮；5-(2-甲氧基-4-甲基苯氧基)呋喃-2(5H)-酮；5-氧代-2,5-二氢呋喃-2-基-2-碘苯甲酸酯；5-氧代-2,5-二氢呋喃-2-基肉桂酸酯；5-氧代-2,5-二氢呋喃-2-基-2-(2,6-二氯苯氧基)乙酸酯；5-氧代-2,5-二氢呋喃-2-基环己酸酯；N,N,N-三甲基-3-((5-氧-2,5-二氢呋喃-2-基)氧基)苯基碘化铵；5-(4-(三甲基硅烷基)苯氧基)呋喃-2(5H)-酮；5-(4-(三氟甲基)苯氧基)呋喃-2(5H)-酮；5-(2,4-二氟苯氧基)呋喃-2(5H)-酮；5-氧代-2,5-二氢呋喃-2-基1-萘甲酸酯；1-(叔丁基)2-(5-氧代-2,5-二氢呋喃-2-基)(2R)-吡咯烷-1,2-二羧酸酯。
本发明的另一个目的是提供所述的2(5H)-呋喃-2-酮衍生物的制备方法，包括：以ROH和5-溴-呋喃-2(5H)-酮为原料，以水和有机溶剂为反应溶剂，在无机碱和相转移催化剂存在的条件下常温反应；反应结束后，反应液用二氯甲烷萃取，有机相用无水硫酸钠干燥，减压蒸馏除去溶剂，硅胶柱层析纯化得到如式Ⅰ所示的2(5H)-呋喃-2-酮衍生物。
其中，R同前述。
所述的水和有机溶剂的体积比为1:1～50:1。所述的有机溶剂选自二氯甲烷、二甲基甲酰胺、四氢呋喃或乙醇。
所述的无机碱、相转移催化剂和5-溴-呋喃-2(5H)-酮的摩尔比是1.25～5:0.05～0.3:1。
所述的无机碱为K2CO3；所述的相转移催化剂为四正丁基溴化铵。
所述的ROH和5-溴-呋喃-2(5H)-酮的摩尔比是0.5～5:1，优选为1:1。
所述的硅胶柱层析的洗脱剂为石油醚:乙酸乙酯＝1～6:1v/v。
发明人将新型独脚金内酯类似物2(5H)-呋喃-2-酮衍生物处理水稻，在100μM或50μM的浓度下进行抑制水稻分蘖的试验，达到了显著的抑制水稻分蘖的效果。因此，本发明的另一个目的是提供所述的2(5H)-呋喃-2-酮衍生物在抑制水稻分蘖的应用。
本发明的有益效果：
本发明2(5H)-呋喃-2-酮衍生物具备抑制水稻分蘖的生物活性。同时，相较于独脚金内酯GR24，结构简单、制备价格低廉，成本不到GR24商品化价格的万分之一，对于水稻分蘖的应用具有潜在的商业化前景。
具体实施方式
下面结合具体实施方案对本发明的技术方案作进一步说明。
实施例1
称取K2CO33(2.5mmol,1.25equiv)和四正丁基溴化铵(0.2mmol,0.1equiv)，加水(10ml)，搅拌至全部溶解，加入溶解在CH2Cl2(5ml)中的2,4-二氯基苯酚(2mmol，1equiv),常温搅拌10min，将溶解在CH2Cl2(5ml)中的5-溴-呋喃-2(5H)-酮(2mmol,1equiv)逐滴加入上述体系中，常温搅拌8h，将反应液用CH2Cl2(3×5ml)萃取，用无水硫酸钠干燥，减压蒸馏除去溶剂，干法拌硅胶、装载样品，用(石油醚/乙酸乙酯＝6:1v/v)作为洗脱剂，分离得到化合物1(白色固体，收率为84％)，鉴定为5-(2,4-二氯苯)呋喃-2(5H)-酮。
1H NMR(400MHz,CDCl3)δ7.57(dd,J＝5.6,1.2Hz,1H),7.37(d,J＝8.1Hz,2H),7.13(t,J＝8.1Hz,1H),6.45(s,1H),6.39(dd,J＝5.6,1.0Hz,1H).13C NMR(101MHz,CDCl3)δ151.6,149.96,134.9,130.4,129.8,125.3,104.58,20.7,16.8.
实施例2
以2,6-二氯苯酚代替实施例1中的2,4-二氯苯酚，其他与实施例1相同，得到化合物2(白色固体，收率为81％)，鉴定为5-(2,6-二氯苯氧基)呋喃-2(5H)-酮。
1H NMR(400MHz,CDCl3)δ7.48(dd,J＝5.7,1.2Hz,1H),7.43(d,J＝2.3Hz,1H),7.28–7.24(m,2H),6.39(dd,J＝5.7,1.1Hz,1H),6.35(d,J＝1.1Hz,1H).13C NMR(101MHz,CDCl3)δ169.9,149.6,148.2,129.3,126.8,125.4,103.0.
实施例3
以2-溴苯酚代替实施例1中的2,4-二氯苯酚，其他与实施例1相同，得到化合物3(白色固体，收率为96％)，鉴定为5-(2-溴苯氧基)呋喃-2(5H)-酮。
1H NMR(400MHz,CDCl3)δ7.53(d,J＝7.6Hz,1H),7.44(dd,J＝5.7,1.2Hz,1H),7.27–7.26(m,2H),7.00–6.96(m,1H),6.33(s,1H),6.29(dd,J＝5.7,1.1Hz,1H).13C NMR(101MHz,CDCl3)δ169.8,152.9,149.8,133.6,128.9,125.4,118.6,113.5,101.3.
实施例4
以2,4-二氟苯氧乙酸代替实施例1中的2,4-二氯苯酚，其他与实施例1相同，得到化合物4(白色固体，收率为91％)，鉴定为5-氧代-2,5-二氢呋喃-2-基-2-(2,4-二氟苯氧基)乙酸酯。
1H NMR(400MHz,CDCl3)δ7.36(dd,J＝5.7,1.3Hz,1H),7.08(t,J＝1.2Hz,1H),7.02–6.96(m,,1H),6.88(ddd,J＝11.2,8.3,3.0Hz,1H),6.83–6.78(m,1H),6.36(dd,J＝5.7,1.1Hz,1H),4.75(s,2H).13C NMR(101MHz,CDCl3)δ169.2,166.9,149.2,125.6,118.3,111.0,105.6,105.3,105.1,94.0,67.3.
实施例5
以3,3,3-三氟丙酸代替实施例1中的2,4-二氯苯酚，其他与实施例1相同，得到化合物5(淡黄色液体，收率为90％)，鉴定为5-氧代2,5-二氢呋喃-2-基3,3,3-三氟丙酸酯。
1H NMR(400MHz,CDCl3)δ7.38(dd,J＝5.7,1.3Hz,1H),7.05(t,J＝1.1Hz,1H),6.39(dd,J＝5.7,1.0Hz,1H),3.32(q,J＝9.7Hz,2H).13C NMR(101MHz,CDCl3)δ169.1,162.5,149.0,125.6,94.1,39.2(dd,J＝70.7,30.3Hz).
实施例6
以1-萘酚代替实施例1中的2,4-二氯苯酚，其他与实施例1相同，得到化合物6(白色固体，收率为78％)，5-(1-萘氧基)呋喃-2(5H)-酮。
1H NMR(400MHz,CDCl3)δ8.18-8.16(m,1H),7.89–7.85(m,1H),7.63(d,J＝8.3Hz,1H),7.57–7.51(m,2H),7.49(dd,J＝5.7,1.2Hz,1H),7.44(t,J＝8.0Hz,1H),7.30(d,J＝7.6Hz,1H),6.55(s,1H),6.39(dd,J＝5.7,1.1Hz,1H).13C NMR(101MHz,CDCl3)δ170.0,152.2,149.9,134.6,127.8,126.8,126.0,125.6,125.3,123.5,121.5,109.7,100.9.
实施例7
以1-溴-2-萘酚代替实施例1中的2,4-二氯苯酚，其他与实施例1相同，得到化合物7(白色固体，收率为85％)，鉴定为5-(1-溴-2-萘氧基)呋喃-2(5H)-酮。
1H NMR(400MHz,CDCl3)δ8.28(d,J＝8.5Hz,1H),7.86(d,J＝8.7Hz,2H),7.65(t,J＝1.1Hz,1H),7.59–7.51(m,3H),6.47(t,J＝1.2Hz,1H),6.40(dd,J＝5.6,1.2Hz,1H).13CNMR(101MHz,CDCl3)δ169.8,151.0,149.7,132.8,131.7,129.4,128.2,126.8,126.0,125.6,119.2,112.6,102.4.
实施例8
以2,6-二溴-4-甲基苯酚代替实施例1中的2,4-二氯苯酚，其他与实施例1相同，得到化合物8(白色固体，收率为79％)，鉴定为5-(2,6-二溴-4-甲基苯氧基)呋喃-2(5H)-酮。
1H NMR(400MHz,CDCl3)δ7.59(dd,J＝5.6,1.2Hz,1H),7.41(d,J＝0.5Hz,2H),6.48(d,J＝1.1Hz,1H),6.41(dd,J＝5.6,1.1Hz,1H),2.35(s,3H).13C NMR(101MHz,CDCl3)δ169.8,149.6,147.8,138.3,133.5,125.4,117.7,103.2,77.5,77.2,76.8,20.4.
实施例9
以4-甲基噻唑-5-甲酸代替实施例1中的2,4-二氯苯酚，其他与实施例1相同，得到化合物9(白色固体，收率为94％)，鉴定为5-氧代-2,5-二氢呋喃-4-甲基噻唑-5-甲酸酯。
1H NMR(400MHz,CDCl3)δ8.87(s,1H),7.46(dd,J＝5.7,1.3Hz,1H),7.19(s,1H),6.41(dd,J＝5.7,1.1Hz,1H),2.80(s,3H).13C NMR(101MHz,CDCl3)δ169.4,163.3,159.9,156.9,149.5,125.6,94.2,17.6.
实施例10
以2-苯基苯甲酸代替实施例1中的2,4-二氯苯酚，其他与实施例1相同，得到化合物10(白色固体，收率为95％)，鉴定为5-氧代-2,5-二氢呋喃-2-基2-(2-苯基)苯甲酸酯。
1H NMR(400MHz,CDCl3)δ7.91(d,J＝7.8Hz,1H),7.59-7.56(m,1H),7.43(t,J＝6.0Hz,1H),7.42–7.36(m,4H),7.29(dd,J＝7.4,1.7Hz,2H),6.92(s,1H),6.85(dd,J＝5.7,1.1Hz,1H),6.12(d,J＝5.6Hz,1H).13CNMR(101MHz,CDCl3)δ169.8,166.4,149.8,143.3,141.1,132.5,131.0,130.6,128.6(d,J＝15.3Hz),128.2,127.5(d,J＝2.7Hz),124.7,94.1.
实施例11
以新戊酸代替实施例1中的2,4-二氯苯酚，其他与实施例1相同，得到化合物12(黄色油状液体，收率为89％)，鉴定为5-氧代2,5-二氢呋喃-2-基新戊酸酯。
1H NMR(400MHz,CDCl3)δ7.36(dd,J＝5.7,1.3Hz,1H),7.01(t,J＝1.2Hz,1H),6.33(dd,J＝5.7,1.1Hz,1H),1.25(s,9H).13C NMR(101MHz,CDCl3)δ176.5,169.8,149.9,125.2,94.0,39.0,26.8.
实施例12
以4-乙基苯酚代替实施例1中的2,4-二氯苯酚，其他与实施例1相同，得到化合物14(黄色油状液体，收率为82％)，鉴定为5-(4-乙基苯氧基)呋喃-2(5H)-酮。
1H NMR(400MHz,CDCl3)δ7.40(dd,J＝5.7,1.1Hz,1H),7.19(d,J＝8.6Hz,2H),7.08(d,J＝8.6Hz,2H),6.41(s,1H),6.34(dd,J＝5.7,1.1Hz,1H),2.65(q,J＝7.6Hz,2H),1.25(t,J＝7.6Hz,3H).13C NMR(101MHz,CDCl3)δ170.1,154.4,145.0,140.0,129.0,125.3,117.1,101.2,28.1,15.8.
实施例13
以3-甲氧基苯酚代替实施例1中的2,4-二氯苯酚，其他与实施例1相同，得到化合物16(黄色油状液体，收率为73％)，鉴定为5-(3-甲氧基苯氧基)呋喃-2(5H)-酮。
1H NMR(400MHz,CDCl3)δ7.38(d,J＝5.5Hz,1H),7.23(t,J＝7.8Hz,1H),6.73(d,J＝7.9Hz,1H),6.67(d,J＝6.9Hz,2H),6.39(s,1H),6.30(d,J＝5.5Hz,1H),3.79(s,3H).13CNMR(101MHz,CDCl3)δ170.0,160.8,157.4,145.0,130.3,125.2,109.4,108.8,103.2,100.6,55.4.
实施例14
以2,4,6-三甲基苯酚代替实施例1中的2,4-二氯苯酚，其他与实施例1相同，得到化合物18(白色固体，收率为61％)，鉴定为5-(2,4,6-三甲苯氧基)呋喃-2(5H)-酮。
1H NMR(400MHz,CDCl3)δ7.45(d,J＝5.6Hz,1H),6.87(s,2H),6.34(d,J＝5.6Hz,1H),6.10(s,1H),2.28(s,6H),2.26(s,3H).13C NMR(101MHz,CDCl3)δ151.6,150.0,134.9,130.4,130.0,125.2,104.5,20.7,16.8.HR-MS(ESI)m/zCalcd.forC13H15O3([M+H]+):219.1021,Found:219.1015.
实施例15
以2-甲氧基-4-甲基苯酚代替实施例1中的2,4-二氯苯酚，其他与实施例1相同，得到化合物19(白色固体，收率为69％)，鉴定为5-(2-甲氧基-4-甲基苯氧基)呋喃-2(5H)-酮。
1H NMR(400MHz,CDCl3)δ7.46(d,J＝5.7Hz,1H),7.12(d,J＝8.1Hz,1H),6.77–6.72(m,2H),6.38(d,J＝1.0Hz,1H),6.30(d,J＝5.7Hz,1H),3.88(s,3H),2.35(s,3H).13C NMR(101MHz,CDCl3)δ150.1,142.5,135.3,125.3,121.3,120.3,113.1,102.3,77.4,77.1,76.7,55.8,21.3.
实施例16
以2-碘苯甲酸代替实施例1中的2,4-二氯苯酚，其他与实施例1相同，得到化合物20(白色固体，收率为94％)，鉴定为5-氧代-2,5-二氢呋喃-2-基-2-碘苯甲酸酯。
1H NMR(400MHz,CDCl3)δ8.04(dd,J＝7.9,0.8Hz,1H),7.88(dd,J＝7.8,1.6Hz,1H),7.51(dd,J＝5.7,1.3Hz,1H),7.46–7.42(m,1H),7.24–7.20(m,2H),6.40(dd,J＝5.7,1.1Hz,1H).13C NMR(101MHz,CDCl3)δ169.6,164.0,149.7,141.9,133.9,132.3,131.8,128.2,125.5,94.9,94.7.
实施例17
以肉桂酸代替实施例1中的2,4-二氯苯酚，其他与实施例1相同，得到化合物21(白色固体，收率为90％)：鉴定为5-氧代-2,5-二氢呋喃-2-基肉桂酸酯。
1H NMR(400MHz,CDCl3)δ7.81(d,J＝16.0Hz,1H),7.56–7.54(m,2H),7.44–7.42(m,4H),7.16(s,1H),6.45(d,J＝16.0Hz,1H),6.37(dd,J＝5.7,1.0Hz,1H).13CNMR(101MHz,CDCl3)δ169.8,164.7,150.0,147.9,133.7,131.2,129.1,128.5,125.3,115.7,94.1.
实施例18
以2,6-二氯苯氧乙酸代替实施例1中的2,4-二氯苯酚，其他与实施例1相同，得到化合物22(白色固体，收率为93％)，鉴定为5-氧代-2,5-二氢呋喃-2-基-2-(2,6-二氯苯氧基)乙酸酯。
1H NMR(400MHz,CDCl3)δ7.42(dd,J＝5.7,1.3Hz,1H),7.32(d,J＝8.1Hz,2H),7.15(t,J＝1.1Hz,1H),7.06(t,J＝8.1Hz,1H),6.37(dd,J＝5.7,1.1Hz,1H),4.74(s,2H).13CNMR(101MHz,CDCl3)δ169.3,166.2,150.0,149.4,129.1,129.1,126.2,125.5,94.0,68.6.
实施例19
以环己甲酸代替实施例1中的2,4-二氯苯酚，其他与实施例1相同，得到化合物23(黄色油状液体，收率为92％)，鉴定为5-氧代-2,5-二氢呋喃-2-基环己酸酯。
1H NMR(400MHz,CDCl3)δ7.34(dd,J＝5.7,0.9Hz,1H),7.01(s,1H),6.32(dd,J＝5.6,0.6Hz,1H),2.39(ddd,J＝14.8,7.4,3.6Hz,1H),1.94–1.92(m,2H),1.77(dd,J＝9.6,6.2Hz,2H),1.67–1.65(m,1H),1.51–1.43(m,2H),1.33–1.21(m,3H).13C NMR(101MHz,CDCl3)δ174.0,169.8,149.9,125.1,93.9,42.8,28.6(d,J＝1.1Hz),25.6,25.2.
实施例20
以3-羟基-N,N,N-三甲基苯基碘化铵代替实施例1中的2,4-二氯苯酚，其他与实施例1相同，得到化合物24(白色固体，收率为82％)，鉴定为N,N,N-三甲基-3-((5-氧-2,5-二氢呋喃-2-基)氧基)苯基碘化铵。
1H NMR(400MHz,D2O)δ7.59(dd,J＝5.8,1.1Hz,1H),7.56–7.48(m,3H),7.33(dd,J＝7.3,1.9Hz,1H),6.72(s,1H),6.38(dd,J＝5.7,1.0Hz,1H),3.56(s,9H).HR-MS(ESI)m/zCalcd.for C13H16NO3([M-I]+):234.1120,Found:234.1124.
实施例21
以4-三甲基硅苯酚代替实施例1中的2,4-二氯苯酚，其他与实施例1相同，得到化合物25(白色固体，收率为78％)，鉴定为5-(4-(三甲基硅烷基)苯氧基)呋喃-2(5H)-酮。
1H NMR(400MHz,CDCl3)δ7.53(d,J＝8.3Hz,2H),7.41(d,J＝4.5Hz,1H),7.16(d,J＝8.3Hz,2H),6.45(s,1H),6.33(d,J＝4.6Hz,1H),0.30(s,9H).13C NMR(101MHz,CDCl3)δ167.0,157.0,149.9,135.4,135.0,125.3,116.3,100.5,-1.0.
实施例22
以4-三氟甲基苯酚代替实施例1中的2,4-二氯苯酚，其他与实施例1相同，得到化合物26(白色固体，收率为77％)，鉴定为5-(4-(三氟甲基)苯氧基)呋喃-2(5H)-酮。
1H NMR(400MHz,CDCl3)δ7.61(d,J＝8.6Hz,2H),7.43(dd,J＝5.7,1.2Hz,1H),7.22(d,J＝8.6Hz,2H),6.47(s,1H),6.37(dd,J＝5.7,1.1Hz,1H).13C NMR(101MHz,CDCl3)δ169.6,149.6,127.2,125.4,120.1,116.7,99.8.
实施例23
以2,4-二氟苯酚代替实施例1中的2,4-二氯苯酚，其他与实施例1相同，得到化合物27(白色固体，收率为76％)，鉴定为5-(2,4-二氟苯氧基)呋喃-2(5H)-酮。
1H NMR(400MHz,CDCl3)δ7.46(dd,J＝5.4,1.3Hz,1H),7.33–7.27(m,1H),6.96–6.83(m,2H),6.38–6.34(m,2H).13C NMR(101MHz,CDCl3)δ169.5,149.4,125.8,122.0,111.2,105.2,102.0.
实施例24
以1-萘基甲酸代替实施例1中的2,4-二氯苯酚，其他与实施例1相同，得到化合物28(白色固体，收率为93％)，鉴定为5-氧代-2,5-二氢呋喃-2-基1-萘甲酸酯。
1H NMR(400MHz,CDCl3)δ8.98(d,J＝8.7Hz,1H),8.26(d,J＝7.3Hz,1H),8.09(d,J＝8.2Hz,1H),7.91(d,J＝8.1Hz,1H),7.69–7.65(m,1H),7.58(t,J＝7.5Hz,1H),7.52-7.49(m,2H),7.35(t,J＝4.7Hz,1H),6.41(d,J＝5.7Hz,1H).13C NMR(101MHz,CDCl3)δ169.6,149.6,133.4,132.6,129.9,128.6,128.3,127.7,127.1,126.4,126.2,125.3,94.1.
实施例25
以Boc-D-脯氨酸代替实施例1中的2,4-二氯苯酚，其他与实施例1相同，得到化合物29(白色固体，收率为92％)，鉴定为1-(叔丁基)2-(5-氧代-2,5-二氢呋喃-2-基)(2R)-吡咯烷-1,2-二羧酸酯。
1H NMR(400MHz,CDCl3)δ7.39–7.10(m,1H),7.06(d,J＝13.5Hz,1H),6.34(dd,J＝12.9,5.6Hz,1H),4.32(ddd,J＝13.1,8.7,3.8Hz,1H),3.60–3.37(m,2H),2.35–2.18(m,1H),2.09–1.87(m,3H),1.48–1.42(m,9H).13C NMR(101MHz,CDCl3)δ171.4,169.7,154.5,149.9,125.5,94.5,80.5,59.1,58.8,46.6,28.3,24.5.
实施例26 2(5H)-呋喃-2-酮衍生物抑制水稻分蘖活性试验
在自然环境条件下，采用全培养液培养水稻，实验组添加DMSO溶解的化合物进行处理，对照组添加同等体积的DMSO。培养一段时间后，同时统计实验组和对照组分蘖数，计算每组数据的平均值，并采用t测验进行分析，比较两个平均数的差异是否显著：当P≤0.05时，认为化合物对水稻分蘖具有显著抑制作用；当P≤0.01时，认为具有极显著抑制作用。
水稻来源于南京农业大学农学院农学系，全部保存于南京农业大学农学院农学系。
供试仪器：SW-CJ-2D双人单面净化工作台，RXZ型智能人工气候培养箱，多参数测试仪，移液枪，中转箱等。
主要试剂：
一、化合物1-化合物3抑制水稻分蘖活性试验
试验材料：“日本晴”水稻。
培养方法：水稻种子经1％过氧化氢浸种1天，清洗数次后，清水浸种至萌发。播种至穴盘，生长至三叶一心期时，选择地上部及根系大小形态均一致的幼苗，移栽至pH＝5.5,氮浓度2mM的木村B营养液中培养至第一个分蘖长出，然后移栽至pH＝5.5,氮浓度4mM的木村B营养液培养，每4天换一次营养液。
处理条件：水稻移栽后，设置实验组：3个处理，分别加入化合物1、2、3(100μM)，更换营养液的同时施加化合物。以只加入溶剂DMSO作为对照组(CK)。每组处理24株水稻。
数据统计：化合物处理20天后，统计分蘖数，计算每组分蘖数的平均值，并采用t测验进行分析(表1)。
表1.化合物1-化合物3施加后水稻的分蘖数
注：编号是每组处理水稻植株的植株编号，下同。
二、化合物4-化合物10、化合物12、化合物14、化合物16、化合物18、化合物19-化合物29抑制水稻分蘖活性试验
试验材料：以水稻品种shiokari为背景的独脚金内酯合成突变体d10(突变体自身不能合成独脚金内酯)。
培养方法：种子经1％过氧化氢浸种1天，清洗数次后，清水浸种至萌发。播种至穴盘，生长至三叶一心期时，选择地上部及根系大小形态均一致的幼苗，在pH5.5,氮浓度2mM的营养液中培养至第一个分蘖长出，然后移栽至pH＝5.5,氮浓度4mM的营养液培养，每4天换一次营养液。
处理条件：水稻移栽后，设置实验组：分别加入受试化合物(50μM)，更换营养液同时施加化合物，共分5批进行(见表2-表6)，每批以只加入溶剂DMSO作为对照组(CK)。
数据统计：化合物处理20天后，统计分蘖数。
表2.化合物4-化合物8施加后水稻的分蘖数
表3.化合物施加后水稻的分蘖数
表4.化合物施加后水稻的分蘖数
注：化合物14处理的6号植株由于病虫害等原因生长不正常，植株死亡。
表5.化合物施加后水稻的分蘖数
表6.化合物施加后水稻的分蘖数
由试验结果可知，当水稻第一个分蘖生长出，用含2(5H)-呋喃-2-酮衍生物的培养液进行培养，定期观察水稻的性状，与对照组相比，本发明25个化合物均能明显的抑制水稻分蘖，特别是化合物1、2、3、4、9、14、18、19、20、22、24、25、26、27、28抑制分蘖效果显著。
Claims (8)
1.如式Ⅰ所示的2(5H)-呋喃-2-酮衍生物：
其中，
R为如式
所示的取代的苯基、
n＝1～3的整数，R1选自F、Cl、Br、C1-C2烷基、卤素取代的C1-C2烷基、C1-C2烷氧基、三甲基硅烷基、N,N,N-三甲基碘代季铵盐，但不包括2,6-二溴-4-甲基苯基、3-甲氧基苯基、对氯代苯基、对甲氧基苯基、3,5-二甲氧基苯基、2,4-二甲氧基苯基、2-碘-3-甲氧基苯基；
m＝0或1，R2选自O或共价键，R3选自卤素取代的苯基、1-萘基、4-甲基-5-噻唑基。
2.根据权利要求1所述的2(5H)-呋喃-2-酮衍生物，其特征在于选自以下化合物：
5-(2,4-二氯苯氧基)呋喃-2(5H)-酮；5-(2,6-二氯苯氧基)呋喃-2(5H)-酮；5-(2-溴苯氧基)呋喃-2(5H)-酮；5-氧代-2,5-二氢呋喃-2-基-2-(2,4-二氟苯氧基)乙酸酯；5-氧代-2,5-二氢呋喃-4-甲基噻唑-5-甲酸酯； 5-(4-乙基苯氧基)呋喃-2(5H)-酮；5-(2,4,6-三甲苯氧基)呋喃-2(5H)-酮；5-(2-甲氧基-4-甲基苯氧基)呋喃-2(5H)-酮；5-氧代-2,5-二氢呋喃-2-基-2-碘苯甲酸酯；5-氧代-2,5-二氢呋喃-2-基-2-(2,6-二氯苯氧基)乙酸酯；N,N,N-三甲基-3-((5-氧-2,5-二氢呋喃-2-基)氧基)苯基碘化铵；5-(4-(三甲基硅烷基)苯氧基)呋喃-2(5H)-酮；5-(4-(三氟甲基)苯氧基)呋喃-2(5H)-酮；5-(2,4-二氟苯氧基)呋喃-2(5H)-酮；5-氧代-2,5-二氢呋喃-2-基1-萘甲酸酯。
3.权利要求1所述的2(5H)-呋喃-2-酮衍生物的制备方法，其特征在于以ROH和5-溴-呋喃-2(5H)-酮为原料，以水和有机溶剂为反应溶剂，在无机碱和相转移催化剂存在的条件下常温反应；反应结束后，反应液用二氯甲烷萃取，有机相用无水硫酸钠干燥，减压蒸馏除去溶剂，硅胶柱层析纯化得到如式Ⅰ所示的2(5H)-呋喃-2-酮衍生物。
其中，R同权利要求1。
4.根据权利要求3所述的2(5H)-呋喃-2-酮衍生物的制备方法，其特征在于所述的水和有机溶剂的体积比为1:1～50:1；所述的有机溶剂选自二氯甲烷、二甲基甲酰胺、四氢呋喃或乙醇。
5.根据权利要求3所述的2(5H)-呋喃-2-酮衍生物的制备方法，其特征在于所述的无机碱、相转移催化剂和5-溴-呋喃-2(5H)-酮的摩尔比是1.25～5:0.05～0.3:1；所述的无机碱为K2CO3；所述的相转移催化剂为四正丁基溴化铵。
6.根据权利要求3所述的2(5H)-呋喃-2-酮衍生物的制备方法，其特征在于所述的ROH和5-溴-呋喃-2(5H)-酮的摩尔比是0.5～5:1。
7.根据权利要求6所述的2(5H)-呋喃-2-酮衍生物的制备方法，其特征在于所述的ROH和5-溴-呋喃-2(5H)-酮的摩尔比是1:1。
8.权利要求1-2任一项权利要求所述的2(5H)-呋喃-2-酮衍生物在抑制水稻分蘖的应用。
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