CN1760188A - N-acyl-2 oxo-1,3-derivatives of thiazolidine, preparation method and usage - Google Patents
N-acyl-2 oxo-1,3-derivatives of thiazolidine, preparation method and usage Download PDFInfo
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- CN1760188A CN1760188A CN 200510061126 CN200510061126A CN1760188A CN 1760188 A CN1760188 A CN 1760188A CN 200510061126 CN200510061126 CN 200510061126 CN 200510061126 A CN200510061126 A CN 200510061126A CN 1760188 A CN1760188 A CN 1760188A
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- thiazoles alkane
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- 238000002360 preparation method Methods 0.000 title claims description 10
- 150000003548 thiazolidines Chemical class 0.000 title 1
- 239000002253 acid Substances 0.000 claims abstract description 7
- 239000003960 organic solvent Substances 0.000 claims abstract description 7
- 150000001263 acyl chlorides Chemical class 0.000 claims abstract description 5
- 238000006482 condensation reaction Methods 0.000 claims abstract description 5
- -1 3-aminomethyl phenyl Chemical group 0.000 claims description 36
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 21
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 16
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 10
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 8
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 claims description 7
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 7
- 239000011230 binding agent Substances 0.000 claims description 6
- 230000000694 effects Effects 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 5
- 125000001340 2-chloroethyl group Chemical group [H]C([H])(Cl)C([H])([H])* 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical group ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- 229960001701 chloroform Drugs 0.000 claims description 4
- 125000001188 haloalkyl group Chemical group 0.000 claims description 4
- GBXQPDCOMJJCMJ-UHFFFAOYSA-M trimethyl-[6-(trimethylazaniumyl)hexyl]azanium;bromide Chemical compound [Br-].C[N+](C)(C)CCCCCC[N+](C)(C)C GBXQPDCOMJJCMJ-UHFFFAOYSA-M 0.000 claims description 4
- 125000004417 unsaturated alkyl group Chemical group 0.000 claims description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 4
- 229920002554 vinyl polymer Polymers 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 2
- 241000221785 Erysiphales Species 0.000 abstract description 4
- 241001124076 Aphididae Species 0.000 abstract description 3
- 241001477931 Mythimna unipuncta Species 0.000 abstract 1
- 230000000844 anti-bacterial effect Effects 0.000 abstract 1
- 239000003899 bactericide agent Substances 0.000 abstract 1
- 239000002917 insecticide Substances 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 description 29
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 21
- 238000005160 1H NMR spectroscopy Methods 0.000 description 16
- 238000000034 method Methods 0.000 description 15
- 230000000855 fungicidal effect Effects 0.000 description 10
- 230000000749 insecticidal effect Effects 0.000 description 10
- 239000012141 concentrate Substances 0.000 description 9
- 239000012044 organic layer Substances 0.000 description 9
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 8
- 238000004440 column chromatography Methods 0.000 description 8
- 238000001816 cooling Methods 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 230000002194 synthesizing effect Effects 0.000 description 8
- 241000196324 Embryophyta Species 0.000 description 7
- 238000003556 assay Methods 0.000 description 7
- 241000409991 Mythimna separata Species 0.000 description 6
- 238000000746 purification Methods 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- 241000123650 Botrytis cinerea Species 0.000 description 5
- 241001330975 Magnaporthe oryzae Species 0.000 description 5
- 241000358422 Nephotettix cincticeps Species 0.000 description 5
- 241000209140 Triticum Species 0.000 description 5
- 235000021307 Triticum Nutrition 0.000 description 5
- 230000002401 inhibitory effect Effects 0.000 description 5
- 229920001817 Agar Polymers 0.000 description 4
- 241001425390 Aphis fabae Species 0.000 description 4
- 241000223195 Fusarium graminearum Species 0.000 description 4
- 244000061456 Solanum tuberosum Species 0.000 description 4
- 235000002595 Solanum tuberosum Nutrition 0.000 description 4
- 239000008272 agar Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 231100000331 toxic Toxicity 0.000 description 4
- 230000002588 toxic effect Effects 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 241001454293 Tetranychus urticae Species 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- 241001480061 Blumeria graminis Species 0.000 description 2
- 241000488583 Panonychus ulmi Species 0.000 description 2
- 241000221696 Sclerotinia sclerotiorum Species 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 239000000575 pesticide Substances 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- 230000003449 preventive effect Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- PPDBOQMNKNNODG-NTEUORMPSA-N (5E)-5-(4-chlorobenzylidene)-2,2-dimethyl-1-(1,2,4-triazol-1-ylmethyl)cyclopentanol Chemical compound C1=NC=NN1CC1(O)C(C)(C)CC\C1=C/C1=CC=C(Cl)C=C1 PPDBOQMNKNNODG-NTEUORMPSA-N 0.000 description 1
- YHOYYHYBFSYOSQ-UHFFFAOYSA-N 3-methylbenzoyl chloride Chemical compound CC1=CC=CC(C(Cl)=O)=C1 YHOYYHYBFSYOSQ-UHFFFAOYSA-N 0.000 description 1
- NQUVCRCCRXRJCK-UHFFFAOYSA-N 4-methylbenzoyl chloride Chemical compound CC1=CC=C(C(Cl)=O)C=C1 NQUVCRCCRXRJCK-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- VGCXGMAHQTYDJK-UHFFFAOYSA-N Chloroacetyl chloride Chemical compound ClCC(Cl)=O VGCXGMAHQTYDJK-UHFFFAOYSA-N 0.000 description 1
- 241001414720 Cicadellidae Species 0.000 description 1
- 241000238631 Hexapoda Species 0.000 description 1
- FPMIAGPUNXEUCZ-UHFFFAOYSA-N Lythidathion Chemical compound CCOC1=NN(CSP(=S)(OC)OC)C(=O)S1 FPMIAGPUNXEUCZ-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 241001558929 Sclerotium <basidiomycota> Species 0.000 description 1
- 239000005859 Triticonazole Substances 0.000 description 1
- 240000006677 Vicia faba Species 0.000 description 1
- 235000010749 Vicia faba Nutrition 0.000 description 1
- 235000002098 Vicia faba var. major Nutrition 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 1
- 239000012346 acetyl chloride Substances 0.000 description 1
- 230000002924 anti-infective effect Effects 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229960004756 ethanol Drugs 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- RZWZRACFZGVKFM-UHFFFAOYSA-N propanoyl chloride Chemical compound CCC(Cl)=O RZWZRACFZGVKFM-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 230000009885 systemic effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Thiazole And Isothizaole Compounds (AREA)
Abstract
A N-acyl-2-oxy-1, 3-thiazolidine derivative is prepared through condensation reaction between 2-oxy-1, 3-thiazolidine and acyl chloride in organic solvent under existence of acid capture, and post-treating. It can be used as the insecticide for aphid, armyworm, etc and the bactericide for powdery mildew, gray mold, etc.
Description
(1) technical field
The present invention relates to a kind of N-acyl group-2-oxo-1,3-thiazoles alkane derivatives, preparation method and its usage.
(2) background technology
Heterogeneous ring compound has been the main flow of novel pesticide development, and in heterogeneous ring compound, again based on nitrogen heterocyclic ring.Thiazole compound is a development in recent years class more rapidly, and many commercial desinsections, sterilization, weedicide belong to such.For example, the sterilant lythidathion with interior absorption of the former industry of Japanese stone company exploitation has the stronger ability of killing for the various insects that traditional sterilant produced resistance; The triticonazole of SUMITOMO CHEMICAL chemical company exploitation in 1974 is a kind of systemic fungicide, and the formation that infect hypha on the spore is adhered in inhibition prevents rice blast.
2-oxo-1,3-thiazoles alkane is not only a useful organic intermediate, and itself has fungicidal activity (JP 53127466).Simultaneously, existing document illustration N-replacement-2-oxo-1,3-thiazoles alkane derivatives has extensive biological activity, is applied to medicine, pesticide field.For example, WO 94/14784 has disclosed a class N-substituted benzyl-2-oxo-1,3-thiazoles alkane derivatives and has had good anti-infection activity; US 4590182, and EP 0206318 has disclosed some N-phosphorylated-2-oxo-1,3-thiazoles alkane derivatives and has good desinsection, killed mite and eelworm-killing activity.
Yet, the bibliographical information of the synthetic and bioactivity research of rarely found relevant N-acyl group-2-oxo-1,3-thiazoles alkane derivatives.
(3) summary of the invention
The object of the invention is to provide a kind of N-acyl group-2-oxo-1,3-thiazoles alkane derivatives, preparation method and its usage.
N-acyl group of the present invention-2-oxo-1,3-thiazoles alkane derivatives is suc as formula shown in (I):
R represents C in its Chinese style (I)
1～C
10Alkyl, haloalkyl or unsaturated alkyl, or C
6～C
10Aryl; It is one of following that R preferably represents: methyl, ethyl, chloromethyl, 2-chloroethyl, vinyl, and one of also preferred representative is following: phenyl, 3-aminomethyl phenyl, 4-aminomethyl phenyl, more preferably represent one of following: methyl, ethyl, chloromethyl, phenyl.
N-acyl group of the present invention-2-oxo-1, the preparation method of 3-tetrahydrothiazole derivates, comprise the steps: suc as formula the 2-oxo-1,3-thiazoles alkane of (II) with suc as formula the acyl chlorides of (III) under the acid binding agent effect, carry out condensation reaction at 0～10 ℃ in organic solvent, aftertreatment gets product;
R represents C in its Chinese style (III)
1～C
10Alkyl, haloalkyl or unsaturated alkyl, or C
6～C
10Aryl.
Reaction equation is:
Described acid binding agent is preferably triethylamine or pyridine.
Described organic solvent is preferably trichloromethane, methylene dichloride or tetrahydrofuran (THF).
Described 2-oxo-1,3-thiazoles alkane: acyl chlorides: the molar ratio of acid binding agent is preferably 1: 1.0～and 1.4: 1.0～2.0.
Consumption of organic solvent is generally 20～50 times of 2-oxo-1,3-thiazoles alkane quality.
Described condensation reaction time was generally 1～20 hour.
Described reaction product aftertreatment can be: with reaction solution washing, organic layer concentrates, and for example column chromatography or recrystallization method separate with purifying and obtain target product N-acyl group-2-oxo-1,3-thiazoles alkane derivatives resistates with currently known methods.Column chromatography or recrystallization solvent for use can be sherwood oil, ethyl acetate, normal hexane, ethanol or their mixed solution.
Described N-acyl group-2-oxo-1,3-thiazoles alkane derivatives is as the application of insectofungicide.Adopt the Potter spray method synthetic compound to be carried out the insecticidal activity assay of mythimna separata (Mythimna separata), adopt the processing plant to connect the worm method has been carried out green rice leafhopper (Nephotettix cincticeps) to the synthetic compound insecticidal activity assay, adopt pickling process that the synthetic compound has been carried out the insecticidal activity assay of black bean aphid (Aphis fabae), adopt pickling process the synthetic compound to be carried out the insecticidal activity assay of two-spotted spider mite (Tetranchus urticae).The result shows that segment bounds (I) compound has certain insecticidal activity to mythimna separata, broad bean aphid, but green rice leafhopper and two-spotted spider mite are not had the activity of killing.
Adopt toxic potato agar substratum (PDA) method that the synthetic compound has been carried out Pyricularia oryzae (Pyricularia oryzae), the fungicidal activity of fusarium graminearum (Gibberella zeae) and botrytis cinerea pers (Botrytis cinerea) is measured, adopt potted plant toxic potato agar substratum (PDA) method that the fungicidal activity that the synthetic compound has carried out Sclerotinia sclerotiorum (Sclerotoniasclerotiorum) is measured, adopt potted plant stem and leaf of Wheat to preserve the spore method fungicidal activity that the synthetic compound has carried out wheat powdery mildew (Blumeria graminis) is measured.The result shows, all have segment bounds (I) compound to show certain inhibition activity to all for the examination bacterial classification, wherein when R was ethyl, compound reached 70% to the inhibiting rate of wheat powdery mildew, when R was chloromethyl, compound reached 55% to the inhibiting rate of botrytis cinerea pers.
(4) embodiment
The invention will be further described below in conjunction with embodiment, but protection scope of the present invention is not limited to this.
Synthesizing of embodiment 1 N-ethanoyl-2-oxo-1,3-thiazoles alkane
2-oxo-1,3-thiazoles alkane (0.52g, 5mmol) and triethylamine (0.71g 7mmol) is dissolved in the 15ml methylene dichloride, stirs.Under the ice bath cooling, and dripping acetyl chloride (0.47g, 6mmol).Dropwise, reacted 4 hours down at 0～10 ℃.Wash three times, the organic layer anhydrous sodium sulfate drying filters, and concentrates.Resistates obtains faint yellow transparent buttery N-ethanoyl-2-oxo-1,3-thiazoles alkane with column chromatography [V (sherwood oil): V (ethyl acetate)=1: 1] separation and purification.Yield is 84.0%.
This compound
1H NMR and IR are as described below:
1H NMR(CDCl
3)δ：2.48(s，3H，-CH
3)，3.31(t，2H，J＝4.5Hz，-SCH
2-)，4.17(t，2H，J＝4.5Hz，-NCH
2-)；
IR v(cm
-1)：3439，2906，1694，1477，1450，1361，1301，1273，1234，1196，1161，1109，1020，1003，896，692，656，603，476；
Synthesizing of embodiment 2 N-propionyl-2-oxo-1,3-thiazoles alkane
2-oxo-1,3-thiazoles alkane (0.52g, 5mmol) and triethylamine (0.71g 7mmol) is dissolved in the 15ml trichloromethane, stirs.Under the ice bath cooling, and the dropping propionyl chloride (0.65g, 7mmol).Dropwise, reacted 6 hours down at 0～10 ℃.Wash three times, the organic layer anhydrous sodium sulfate drying filters, and concentrates.Resistates obtains faint yellow transparent buttery N-propionyl-2-oxo-1,3-thiazoles alkane with column chromatography [V (sherwood oil): V (ethyl acetate)=1: 1] separation and purification.Yield is 81.0%.
This compound
1H NMR and IR are as described below,
1H NMR(CDCl
3)δ：1.07(t，3H，J＝4.5Hz，-CH
3)，2.78～2.83(q，2H，-CH
2-)，3.26(t，2H，J＝4.5Hz，-SCH
2-)，4.12(t，2H，J＝4.5Hz，-NCH
2-)；
IR v(cm
-1)：3378，2981，2941，1692，1446，1359，1286，1233，1174，1114，1094，1038，1019，963，867，805，706，579；
Synthesizing of embodiment 3 N-chloracetyl-2-oxo-1,3-thiazoles alkane
2-oxo-1,3-thiazoles alkane (0.52g, 5mmol) and pyridine (0.55g 7mmol) is dissolved in the 20ml methylene dichloride, stirs.Under the ice bath cooling, and the dropping chloroacetyl chloride (0.68g, 6mmol).Dropwise, reacted 6 hours down at 0～10 ℃.Wash three times, the organic layer anhydrous sodium sulfate drying filters, and concentrates.Resistates obtains the canescence crystal with re-crystallizing in ethyl acetate, i.e. N-chloracetyl-2-oxo-1,3-thiazoles alkane.Fusing point: 72-74 ℃; Yield is 74.0%.
This compound
1H NMR and IR are as described below,
1H NMR(CDCl
3)δ：3.41(t，2H，J＝4.5Hz，-SCH
2-)，4.24(t，2H，J＝4.5Hz，-NCH
2-)，4.70(s，2H，ClCH
2)；
IR v(cm
-1)：3358，3006，2958，1713，1685，1471，1448，1368，1323，1236，1178，1019，972，901，863，783，727，708，655，640，556，466；
Synthesizing of embodiment 4 N-(3-chlorine propionyl)-2-oxo-1,3-thiazoles alkane
2-oxo-1,3-thiazoles alkane (5mmol) and pyridine (7mmol) are dissolved in the 15ml tetrahydrofuran (THF), stir.The ice bath cooling drips 3-chlorpromazine chloride (6mmol) down.Dropwise, reacted 10 hours down at 0～10 ℃.Wash three times, the organic layer anhydrous sodium sulfate drying filters, and concentrates.Resistates obtains faint yellow transparent buttery N-(3-chlorine propionyl)-2-oxo-1,3-thiazoles alkane with column chromatography [V (sherwood oil): V (normal hexane)=1: 1] separation and purification.Yield is 57.0%.
This compound
1H NMR and IR are as described below,
1H NMR(CDCl
3)δ：1.26(t，2H，J＝4.5Hz，-COCH
2-)，3.34(t，2H，J＝4.5Hz，-SCH
2-)，3.77(t，2H，J＝4.2Hz，-CH
2Cl)，4.23(t，2H，J＝4.5Hz，-NCH
2-)；
IR v(cm
-1)：2953，1682，1619，1405，1360，1315，1242，1178，1066，1018，976，874，793，708，657；
Synthesizing of embodiment 5 N-(2-acryl)-2-oxo-1,3-thiazoles alkane
2-oxo-1,3-thiazoles alkane (5mmol) and triethylamine (8mmol) are dissolved in the 25ml trichloromethane, stir.The ice bath cooling drips 2-acrylate chloride (6mmol) down.Dropwise, reacted 6 hours down at 0～10 ℃.Wash three times, the organic layer anhydrous sodium sulfate drying filters, and concentrates.Resistates obtains faint yellow transparent buttery N-(2-acryl)-2-oxo-1,3-thiazoles alkane with column chromatography [V (sherwood oil): V (ethyl acetate)=2: 1] separation and purification.Yield is 51.0%.
This compound
1H NMR and IR are as described below,
1H NMR (CDCl
3) δ: 3.34 (t, 2H, J=4.5Hz ,-SCH
2-), 4.22 (t, 2H, J=4.5Hz ,-NCH
2-), 5.85～5.88 (q, 1H ,=CH
2In with-trans the H of CO), 6.47～6.51 (q, 1H ,=CH
2In with-CO cis H), 7.22～7.29 (q, 1H ,-CH);
IR v(cm
-1)：2924，1682，1619，1405，1359，1315，1242，1179，1067，1018，977，875，793，708，657；
Synthesizing of embodiment 6 N-benzoyl-2-oxo-1,3-thiazoles alkane
2-oxo-1,3-thiazoles alkane (5mmol) and triethylamine (7mmol) are dissolved in the 20ml methylene dichloride, stir.The ice bath cooling drips Benzoyl chloride (6mmol) down.Dropwise, reacted 8 hours down at 0～10 ℃.Wash three times, the organic layer anhydrous sodium sulfate drying filters, and concentrates.Resistates obtains white crystal with the dehydrated alcohol recrystallization, i.e. N-benzoyl-2-oxo-1,3-thiazoles alkane.Fusing point: 120-122 ℃; Yield is 90.0%.
This compound
1H NMR and IR are as described below,
1H NMR(CDCl
3)δ：3.37(t，2H，J＝4.4Hz，-SCH
2-)，4.22(t，2H，J＝4.4Hz，-NCH
2-)，7.40～7.65(m，5H，-Ph)；
IR v(cm
-1)：1702，1674，1444，1360，1314，1299，1227，1159，1078，1022，966，836，789，733，698，646；
Synthesizing of embodiment 7 N-(3-methyl benzoyl)-2-oxo-1,3-thiazoles alkane
2-oxo-1,3-thiazoles alkane (5mmol) and pyridine (7mmol) are dissolved in the 15ml tetrahydrofuran (THF), stir.The ice bath cooling drips 3-methyl benzoyl chloride (6mmol) down.Dropwise, reacted 12 hours down at 0～10 ℃.Wash three times, the organic layer anhydrous sodium sulfate drying filters, and concentrates.Resistates obtains faint yellow transparent buttery N-(3-methyl benzoyl)-2-oxo-1,3-thiazoles alkane with column chromatography [V (sherwood oil): V (ethyl acetate)=3: 1] separation and purification.Yield is 73.0%.
This compound
1H NMR and IR are as described below,
1H NMR(CDCl
3)δ：2.37(s，3H，-CH
3)，3.34(t，2H，J＝4.4Hz，-SCH
2-)，4.19(t，2H，J＝4.4Hz，-NCH
2-)，7.20～7.44(m，4H，-Ph)；
IR v(cm
-1)：3349，2922，1713，1682，1443，1358，1302，1227，1184，1147，892，799，785，742，695，653；
Synthesizing of embodiment 8 N-(4-methyl benzoyl)-2-oxo-1,3-thiazoles alkane
2-oxo-1,3-thiazoles alkane (5mmol) and triethylamine (6mmol) are dissolved in the 20ml methylene dichloride, stir.The ice bath cooling drips 4-methyl benzoyl chloride (6mmol) down.Dropwise, reacted 12 hours down at 0～10 ℃.Wash three times, the organic layer anhydrous sodium sulfate drying filters, and concentrates.Resistates obtains faint yellow transparent buttery N-(4-methyl benzoyl)-2-oxo-1,3-thiazoles alkane with column chromatography [V (sherwood oil): V (ethyl acetate)=3: 1] separation and purification.Yield is 70.0%.
This compound
1H NMR and IR are as described below,
1H NMR(CDCl
3)δ：2.40(s，3H，-CH
3)，3.39(t，2H，J＝4.5Hz，-SCH
2-)，4.23(t，2H，J＝4.5Hz，-NCH
2-)，7.21～8.01(m，4H，-Ph)；
IR v(cm
-1)：2982，1786，1719，1612，1447，1367，1275，1178，1106，1023，842，754；
The test of embodiment 9 insecticidal activities
Adopt the Potter spray method that embodiment 1～8 synthetic compound has been carried out the insecticidal activity assay of mythimna separata (Mythimnaseparata), working concentration is 1000mg/L; Adopt to handle plant and connect the worm method synthetic compound has been carried out the insecticidal activity assay of green rice leafhopper (Nephotettix cincticeps), working concentration is 500mg/L; Adopt dipping plant method that the synthetic compound has been carried out the insecticidal activity assay of black bean aphid (Aphis fabae) and red spider (Tetranychus urticae), working concentration is 500mg/L.Test result sees Table 1.
The insecticidal activity of table 1 N-acyl group-2-oxo-1,3-thiazoles alkane derivatives
| The embodiment title | Compound/R | Mythimna separata | Aphid | Leafhopper | Red spider |
| Mortality ratio (%) | Mortality ratio (%) | Mortality ratio (%) | Mortality ratio (%) | ||
| Embodiment 1 | Methyl | 23.81 | 51.86 | 0 | 0 |
| Embodiment 2 | Ethyl | 0 | 0 | 0 | 0 |
| Embodiment 3 | Chloromethyl | 16.67 | 22.22 | 0 | 0 |
| Embodiment 4 | The 2-chloroethyl | 0 | 0 | 0 | 0 |
| Embodiment 5 | Vinyl | 13.5 | 27.50 | 0 | 0 |
| Embodiment 6 | Phenyl | 0 | 7.90 | 0 | 0 |
| Embodiment 7 | The 3-aminomethyl phenyl | 17.5 | 20.30 | 0 | 0 |
| Embodiment 8 | The 4-aminomethyl phenyl | 10.0 | 15.56 | 2.6 | 0 |
| - | Blank | 0 | 0 | 0 | 0 |
The test of embodiment 10 fungicidal activities
Adopt toxic potato agar substratum (PDA) method that the fungicidal activity that embodiment 1～8 synthetic compound has carried out Pyricularia oryzae (Pyricularia oryzae), fusarium graminearum (Gibberella zeae) and botrytis cinerea pers (Botrytis cinerea) is measured, general sieve concentration is 25ppm; Adopt potted plant toxic potato agar substratum (PDA) method that the fungicidal activity that the synthetic compound has carried out Sclerotinia sclerotiorum (Sclerotonia sclerotiorum) is measured, general sieve concentration is 500ppm; Adopt potted plant stem and leaf of Wheat to preserve the spore method fungicidal activity that the synthetic compound has carried out wheat powdery mildew (Blumeriagraminis) is measured, general sieve concentration is 500ppm.Test result sees Table 2.
The fungicidal activity of table 2 N-acyl group-2-oxo-1,3-thiazoles alkane derivatives
| The embodiment title | Compound/R | Gibberellic hypha | Pyricularia oryzae | Ash arrhizus bacteria | The sclerotium germ | The white powder germ |
| Inhibiting rate (%) | Inhibiting rate (%) | Inhibiting rate (%) | Preventive effect (%) | Preventive effect (%) | ||
| Embodiment 1 | Methyl | 4.5 | 0 | 0 | 0 | 10.0 |
| Embodiment 2 | Ethyl | 4.5 | 3.5 | 6.3 | 0 | 70.0 |
| Embodiment 3 | Chloromethyl | 4.5 | 0 | 55.0 | 40.0 | 20.0 |
| Embodiment 4 | The 2-chloroethyl | 0 | 14.0 | 4.4 | 22.0 | 0 |
| Embodiment 5 | Vinyl | 10.0 | 17.5 | 5.5 | 10.0 | 40.0 |
| Embodiment 6 | Phenyl | 4.5 | 52.6 | 19.1 | 0 | 25.0 |
| Embodiment 7 | The 3-aminomethyl phenyl | 0 | 26.8 | 10.5 | 0 | 15.0 |
| Embodiment 8 | The 4-aminomethyl phenyl | 0 | 21.1 | 4.4 | 0 | 0 |
| - | Blank | 0 | 0 | 0 | 0 | 0 |
Claims (10)
1, a kind of N-acyl group-2-oxo-1,3-thiazoles alkane derivatives suc as formula (I):
R represents C in its Chinese style (I)
1～C
10Alkyl, haloalkyl or unsaturated alkyl, or C
6～C
10Aryl.
2, N-acyl group as claimed in claim 1-2-oxo-1,3-thiazoles alkane derivatives is characterized in that described R representative is one of following: methyl, ethyl, chloromethyl, 2-chloroethyl, vinyl.
3, N-acyl group as claimed in claim 1-2-oxo-1,3-thiazoles alkane derivatives is characterized in that described R representative is one of following: phenyl, 3-aminomethyl phenyl, 4-aminomethyl phenyl.
4, N-acyl group as claimed in claim 1-2-oxo-1,3-thiazoles alkane derivatives is characterized in that described R representative is one of following: methyl, ethyl, chloromethyl, phenyl.
5, the described N-acyl group of a kind of claim 1-2-oxo-1, the preparation method of 3-tetrahydrothiazole derivates, comprise the steps: 2-oxo-1 suc as formula (II), the 3-thiazolidine with suc as formula the acyl chlorides of (III) under the acid binding agent effect, carry out condensation reaction at 0～10 ℃ in organic solvent, aftertreatment gets product;
R represents C in its Chinese style (III)
1～C
10Alkyl, haloalkyl or unsaturated alkyl, or C
6～C
10Aryl.
6, preparation method as claimed in claim 5 is characterized in that described acid binding agent is triethylamine or pyridine.
7, preparation method as claimed in claim 5 is characterized in that described organic solvent is trichloromethane, methylene dichloride or tetrahydrofuran (THF).
8, preparation method as claimed in claim 5, it is characterized in that described 2-oxo-1,3-thiazoles alkane: acyl chlorides: the molar ratio of acid binding agent is 1: 1.0～1.4: 1.0～2.0, consumption of organic solvent is 20～50 times of 2-oxo-1,3-thiazoles alkane quality.
9,, it is characterized in that described condensation reaction time is 1～20 hour as the described preparation method of one of claim 5～8.
10, the described N-acyl group of claim 1-2-oxo-1,3-thiazoles alkane derivatives is as the application of insectofungicide.
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