Essentials of Heterocyclic Chem IV

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杂环化学概要1 Essentials of Heterocycles I

Imidazole pKa: 6.9, 14.4, 33.7
HN
2
4 5 2
3
N N N1 H
4 5
N
N N O1
4 2N 5
N N1 H
4 5
5
N7 H
N1 H
Purine pKa: 2.5, 8.9
Imidazolidine
4 3 2 3 2 5 6 7 8 9
Tetrazole pKa: 4.9
ED50: Dose required to yield maximum therapeutic effect in 50% of test animals. Efficacy: Description of the relative intensity with which agonists vary in the response they produce, even with similar affinity. Homologue: A compound belonging to a series of compounds differing from each other by a repeating unit (i.e. a CH2, a peptide residue, etc.). Intrinsic activity: The maximal stimulatory response induced by a compound relative to that of a given reference comopund. LD50: Dose required to kill 50% of test animals. Partition coefficient (LogP): Measure of the solubiliity of a compound in water, by its partitioning between 1-octanol and water. A LogP<1 means that a compound is more soluble in water than in 1-octanol. Pharmacophore: The ensemble of steric and electronic features that is necessary to ensure the optimal supramolecular interactions with a specific biological target structure and to trigger (or block) its biological response. This is not a real molecule or moiety, but rather an abstract concept that is considered the largest common denominator shared by a set of active molecules. Potency: The dose of a drug required to produce a specific effect of given intensity as compared to a standard reference. Therapeutic index: LD50/ED50

J. Heterocyclic Chem., 47, 1269 (2010).

4-(Coumarin-3-yl)thiazol-2-ylhydrazone DerivativesFranco Chimenti,a Bruna Bizzarri,a *Adriana Bolasco,a Daniela Secci,aPaola Chimenti,a Arianna Granese,a Simone Carradori,a Melissa D’Ascenzio,aM.Maddalena Scaltrito,b and Francesca Sisto baDipartimento di Chimica e Tecnologie del Farmaco,University ‘‘La Sapienza,’’P.le A.Moro 5,00185Rome,ItalybDipartimento di Sanita`Pubblica-Microbiologia-Virologia,Universita `degli Studi di Milano,via Pascal 36,20133Milan,Italy *E-mail:zarri@uniroma1.itReceived January 13,2010DOI 10.1002/jhet.464Published online 20August 2010in Wiley Online Library().A novel class of coumarin-thiazole conjugated systems (1–31)were synthesized by Hantzsch conden-sation between a -bromo-3-acetyl coumarin and several thiosemicarbazone intermediates.This scaffold was also evaluated for selective antibacterial activity against 20isolates of H.pylori clinical strains,including four metronidazole resistant ones.J.Heterocyclic Chem.,47,1269(2010).INTRODUCTIONHelicobacter pylori are spiral-shaped Gram-negative bacteria with polar ﬂagella that live near the surface of the human gastric mucosa.They have evolved speciﬁc mechanisms to avoid the bactericidal acid environment in the gastric lumen to survive near,to attach to,and to communicate with the human gastric epithelium and host immune system.This interaction sometimes results in severe gastric pathology.In fact,H.pylori infection is indeed the most known risk factor for the development of gastroduodenal ulcers,gastric adenocarcinoma,and gastric mucosa-associated lymphoid tissue lymphoma.H.pylori infections are difﬁcult to cure and success-ful treatment generally requires the simultaneous som-ministration of several antibacterial agents.Antibiotic resistance has resulted in unsatisfactory eradication with dual and now triple therapy in many countries.Newer antibiotics and changes in dosing and duration of therapy may overcome resistant strains but may only provide limited improvement in eradication rates [1–3].In our previous works [4,5]and from the analysis of the structure of natural coumarins reported as potentanti-H .pylori agents [6],we have pointed out that the coumarin ring might play an important role in determin-ing activity and seemed to be crucial for the selective antimicrobial activity of such compounds.Recently,we have synthesized and chemically and biologically char-acterized some new conjugated coumarin-thiazole sys-tems,which were endowed with interesting industrial properties and especially antimicrobial activity on H.pylori clinical strains [7].Furthermore,interest in these structures has renewed due to the recent discovery of their promising antibacte-rial,antifungal,and antimycobacterial activity [8–11].Moving from these indications,in this report we described the synthesis and selective antimicrobial evalu-ation of a new series of 4-(coumarin-3-yl)thiazol-2-ylhy-drazone derivatives which differ for the electronic and steric characteristics on the hydrazone nitrogen (aliphatic chains,cycloaliphatic moiety,and heterocyclic rings).RESULTS AND DISCUSSIONThe coumarin-thiazole derivatives (1–30)were pre-pared in high yields (69–99%)according to a protocolused in our laboratory(Table1).Different carbonyl compounds reacted directly with thiosemicarbazide in ethanol with catalytic amounts of acetic acid,and the obtained thiosemicarbazones were subsequently con-verted into4-(coumarin-3-yl)-2-thiazolylhydrazones by reaction with a-bromo-3-acetyl coumarin in the same solvent at room temperature(Hantzsch condensation).a-Bromo-3-acetyl coumarin has been synthesized by direct halogenation of3-acetyl coumarin with bromine in chlo-roform.Moreover,knowing that all reported structures possess an imine bond,which could be hydrolyzed in the acidic environment of the stomach(reproduced in the biological assay),we also synthesized and assayed their common intermediate(31)by direct reaction between thiosemicabazide and a-bromo-3-acetyl couma-rin in ethanol at room temperature.All synthesized products were puriﬁed with petroleum ether and diethyl ether and,if requested,by chromatog-raphy before characterization by spectroscopic methods (IR and1H NMR)and elemental analysis.The com-pounds,correctly analyzed for their molecular formula, showed in the IR spectrum strong bands at1710and 1600cmÀ1due to the presence of a d-lactone C¼¼O and C¼¼N group,respectively.Moreover,the presence of a C¼¼N double bond can give rise to isomeric geometry E/Z.The1H NMR(in CDCl3)spectra analysis revealed that the E isomer was more favored and stable than the Z-conﬁguration.The amounts of both conformers were measured by area integration of the signal relative to the CH3(R1)protons (area ratio of proton signals E:Z was generally6:1).The low-ﬁeld signal was assigned to the E isomer,as it is widely accepted in thiosemicarbazone derivatives[17]. Our choice,as reaction medium,of a polar alcoholic solvent appeared to be preferred to obtain the E-conﬁgu-ration and limit the interconversion according to the results of our previous theoretical and chromatographic study for similar compounds[18].Then,all compounds were evaluated,as mixture of E/ Z conformers,against20clinical strains of H.pylori, which are more resistant to conventional therapy.Metro-nidazole was used as standard antibacterial drug(Table 2).Most of the assayed compounds showed no anti-H. pylori activity or comparable activity with respect to Metronidazole(MIC!16l g/mL).Only some com-pounds(14,21,and26),bearing a speciﬁc heterocyclic ring(furan,pyridine,and naphthalene)on the hydrazone nitrogen,possessed MIC values slightly inferior to the reference drug(MIC¼8l g/mL)against some clinical H.pylori strains.Unfortunately,it was not possible to correlate this biological activity with lipophilicity (Clog P).EXPERIMENTALThe chemicals,solvents for synthesis and spectral grade sol-vents were purchased from Aldrich(Italy)and used without further puriﬁcation.Melting points are uncorrected and were determined automatically on an FP62apparatus(Mettler-Tol-edo).1H NMR spectra were recorded at400MHz on a Bruker spectrometer.Chemical shifts are expressed as d units(parts per millions)relative to the solvent peak.Coupling constants J are valued in Hertz(Hz).IR spectra were registered on a Per-kin Elmer FTIR Spectrometer Spectrum1000in KBr.Elemen-tal analysis for C,H,and N were recorded on a Perkin-Elmer 240B microanalyzer and the analytical results were within 60.4%of the theoretical values for all compounds.All reac-tions were monitored by TLC performed on0.2-mm-thick silica gel plates(60F254Merck).Lipophilicity parameter, Clog P,has been calculated for each molecule by using Chem-Draw ultra8.0.The synthesis of some compounds has been described in previous references(Table1)and was performed with slight changes.Their analytical and spectral data were in full agreement with those reported in the literature.Typical procedure for the thiosemicarbazones synthesis.The appropriate carbonylic compound(50mmol) was dissolved in100mL of ethanol and stirred vigorously atTable1Structure of derivatives1–31.Comp R R11[ref.12]CH3CH32CH2CH3CH33CH(CH3)2CH34(CH2)2CH3CH35CH2CH3CH2CH36(CH2)2CH¼CH2CH37(CH2)4CH3CH38(CH2)3CH3CH2CH39(CH2)5CH3CH3102-CH3-Cyclopentyliden113-CH3-Cyclopentyliden12Cyclooctyliden13Cyclohexyl CH314[ref.11]Fur-2-yl H15Fur-2-yl CH316Tiophen-2-yl H17Tiophen-2-yl CH318[ref.13]Phenyl CH319Pyridin-2-yl CH320Pyridin-3-yl H21Pyridin-3-yl CH322Pyridin-4-yl H23Pyridin-4-yl CH3241H-indol-3-yl H25[ref.14]3,4-Methylendioxophenyl H26Naphtalen-1-yl H27Naphtalen-2-yl CH328[ref.15]Coumarin-3-yl CH3292-COOH-9H-ﬂuoren-5-yliden30Thiazol-2-yl CH331[ref.16]H HS.Carradori,M.D’Ascenzio,M.Maddalena Scaltrito,and F.Sistoroom temperature with an equimolar amount of thiosemicarba-zide for24h with catalytic amount of acetic acid.The desired thiosemicarbazone precipitated from reaction mixture wasﬁl-tered and crystallized from suitable solvent and dried. Typical procedure for the Hantzsch protocol for the preparation of derivatives1–30.Equimolar amounts of theprepared thiosemicarbazones(50mmol)and freshly synthe-sized3-a-bromo-acetyl coumarin(50mmol),both dissolved in ethanol,were reacted at room temperature under magnetic stir-ring for4h.The precipitate wasﬁltered and dried to give compounds1–30in69–99%yield.3-(2-(2-Butylidenehydrazynyl)thiazol-4-yl)-2H-chromen-2-one(2).Light brown crystals,96%yield,mp205–210 C;1H NMR(CDCl3):d1.15–1.18(t,3H,J¼7.2,CH3),2.20(s,3H, CH3),2.42–2.47(q,2H,J¼7.2,CH2),7.35–7.39(m,1H,J7-6¼J7-8¼7.8Hz,J7-5¼2.3Hz,C7H-chrom),7.41–7.43(dd, 1H,J5-6¼7.9,J5-7¼2.4Hz,C5H-chrom),7.62–7.65(m,1H, J6-5¼J6-7¼7.8Hz,J6-8¼2.3Hz,C6H-chrom),7.68(s,1H, C5H-thiaz.),7.77–7.83(dd,1H,J8-7¼7.8Hz,J8-6¼2.2Hz, C8H-chrom.),10.75(bs,1H,NH,D2O exch.);Anal.Calcd.for C15H13N3O2S:C,60.18;H,4.38;N,14.04.Found:C,60.13; H,4.37;N,14.06.3-(2-(2-(3-Methyl-2-butylidene)hydrazynyl)thiazol-4-yl)-2H-chromen-2-one(3).Yellow crystals,99%yield,mp170–173 C;1H NMR(CDCl3):d0.95–0.97(d,J¼6.6Hz,6H,2ÂCH3),1.98–2.11(m,J¼6.6Hz,1H,CH),2.17(s,3H, CH3),7.35–7.38(m,J7-6¼J7-8¼7.3Hz,J7-5¼1.8Hz,1H, C7H-chrom.),7.39–7.41(dd,J5-6¼7.3Hz,J5-7¼1.8Hz,1H, C5H-chrom.),7.61–7.65(m,J6-5¼J6-7¼7.3Hz,J6-8¼1.8 Hz,1H,C6H-chrom.),7.79–7.82(dd,J8-7¼7.3Hz,J8-6¼1.9 Hz,1H,C8H-chrom.),7.84(s,1H,C5H-thiaz.),8.54(s,1H, C4H-chrom.),12.00(br s,1H,NH,D2O exch.);Anal.Calcd. for C17H17N3O2S:C,62.36;H, 5.23;N,12.83.Found:C, 62.41;H,5.24;N,12.82.3-(2-(2-(2-Pentanylidene)hydrazynyl)thiazol-4-yl)-2H-chro-men-2-one(4).Orange crystals,82%yield,mp186–187 C; 1H NMR(CDCl3):d0.97–1.03(t,J¼7.4Hz,3H,CH3), 1.59–1.65(m,J¼7.4Hz,J¼5.6Hz,2H,CH2),2.18(s,3H, CH3),2.33–2.38(t,J¼5.6Hz,2H,CH2),7.34–7.37(m,J7-6¼J7-8¼7.6Hz,J7-5¼2.1Hz,1H,C7H-chrom.),7.62–7.65 (dd,J5-6¼7.6Hz,J5-7¼2.2Hz,1H,C5H-chrom.),7.68–7.75 (m,J6-5¼J6-7¼7.7Hz,J6-8¼2.1Hz,1H,C6H-chrom.), 7.77–7.81(dd,J8-7¼7.8Hz,J8-6¼2.1Hz,1H,C8H-chrom.), 7.85(s,1H,C5H-thiaz.),8.62(s,1H,C4H-chrom.),11.90(br s,1H,NH,D2O exch.);Anal.Calcd.for C17H17N3O2S:C, 62.36;H,5.23;N,12.83.Found:C,62.39;H,5.22;N,12.83. 3-(2-(2-(3-Pentanylidene)hydrazynyl)thiazol-4-yl)-2H-chro-men-2-one(5).Yellow crystals,82%yield,mp180–183 C; 1H NMR(CDCl3):d1.16–1.19(t,J¼7.3Hz,6H,2ÂCH3), 2.40–2.46(m,4H,2ÂCH2),7.35–7.37(m,J7-6¼J7-8¼6.8 Hz,J7-5¼1.4Hz,1H,C7H-chrom.),7.38–7.41(dd,J5-6¼6.8 Hz,J5-7¼1.4Hz,1H,C5H-chrom.),7.59–7.63(m,J6-5¼J6-7¼6.8Hz,J6-8¼1.4Hz,1H,C6H-chrom.),7.78–7.80(dd,J8-7¼6.8Hz,J8-6¼1.4Hz,1H,C8H-chrom.),7.84(s,1H, C5H-thiaz.),8.61(s,1H,C4H-chrom.),12.01(br s,1H,NH, D2O exch.);Anal.Calcd.for C17H17N3O2S:C,62.36;H,5.23; N,12.83.Found:C,62.38;H,5.24;N,12.82.3-(2-(2-(5-Hexen-2-ylidene)hydrazynyl)thiazol-4-yl)-2H-chromen-2-one(6).Light yellow crystals,73%yield,mp 195–197 C;1H NMR(CDCl3):d2.19(s,3H,CH3),2.38–2.45 (t,J¼6.5Hz,2H,CH2),2.48–2.53(m,J¼6.5Hz,J¼7.2 Hz,2H,CH2),5.05–5.08(dd,J cis¼8.8Hz,J gem¼1.7Hz, 1H,CH¼¼),5.09–5.13(dd,J trans¼17.7Hz,J gem¼1.7Hz, 1H,CH¼¼),5.78–5.85(m,J cis¼8.8Hz,J trans¼17.8Hz,J¼7.2Hz1H,CH¼¼),7.36–7.40(m,J7-6¼J7-8¼7.5,J7-5¼1.5,1H,C7H-chrom.),7.41–7.43(dd,J5-6¼7.5,J5-7¼1.5, 1H,C5H-chrom.),7.62–7.64(m,J6-5¼J6-7¼7.5,J6-8¼1.4, 1H,C6H-chrom.),7.79–7.81(dd,J8-7¼7.6,J8-6¼1.4,1H, C8H-chrom.),7.86(s,1H,C5H-thiaz.),8.61(s,1H,C4H-chrom.),12.00(br s,1H,NH,D2O exch.);Anal.Calcd.for C18H17N3O2S:C,63.70;H,5.05;N,12.38.Found:C,63.75; H,5.04;N,12.38.3-(2-(2-(2-Heptanylidene)hydrazynyl)thiazol-4-yl)-2H-chro-men-2-one(7).Yellow crystals,99%yield,mp198–201 C; 1H NMR(DMSO-d6):d0.93–0.95(m,3H,CH3),1.22–1.30 (m,2H,CH2), 1.32–1.38(m,2H,CH2),1.55–1.61(m,2H, CH2),2.18(s,3H,CH3),2.36–2.40(m,2H,CH2),7.37–7.39 (m,J7-6¼J7-8¼7.1Hz,J7-5¼3.7Hz,1H,C7H-chrom.), 7.40–7.42(dd,J5-6¼7.16,J5-7¼3.8,1H,C5H-chrom.), 7.61–7.66(m,J6-5¼J6-7¼7.2Hz,J6-8¼3.8Hz,1H,C6H-chrom.),7.79–7.81(dd,J8-7¼7.1,J8-6¼3.7,1H,C8H-chrom.),7.84(s,1H,C5H-thiaz.),8.61(s,1H,C4H-chrom.), 12.06(br s,1H,NH,D2O exch.);Anal.Calcd.for C19H21N3O2S:C,64.20;H,5.95;N,11.82.Found:C,64.15; H,5.93;N,11.84.Table2MIC values(l g/mL)of derivatives1–31and M(metronidazole)against20H.pylori strains.Compound Metronidazole sensitivestrains(16strains)Metronidazole resistantstrains(4strains)1!16>162!16>163!16>164!16>165!16>166!16!167!16!168!16!169!16!1610!16!1611!16!1612!16!1613!16>16148–!168–!1615!16!1616>16!1617!16!1618!16>1619!16!1620!16!16218–!16!1622!16!1623!16!1624>16!1625!16!16268–!16!1627!16!1628>16>1629!16>1630>16>1631!16>16M0.5–16>164-(Coumarin-3-yl)thiazol-2-ylhydrazone Derivatives3-(2-(2-(3-Heptanylidene)hydrazynyl)thiazol-4-yl)-2H-chro-men-2-one (8).Yellow crystals,77%yield,mp 175–180 C;1H NMR (CDCl 3):d 0.95–0.98(m,3H,CH 3),1.13–1.19(m,2H,CH 2),1.34–1.40(m,2H,CH 2),1.55–1.62(m,3H,CH 3),2.39–2.42(m,2H,CH 2),2.45–2.51(m,2H,CH 2),7.36–7.38(m,1H,C 7H-chrom.),7.39–7.41(m,1H,C 5H-chrom.),7.60–7.64(m,1H,C 6H-chrom.),7.79–7.82(m,1H,C 8H-chrom.),7.83(s,1H,C 5H-thiaz.),8.61(s,1H,C 4H-chrom.),12.14(br s,1H,NH,D 2O exch.);Anal.Calcd.for C 19H 21N 3O 2S:C,64.20;H, 5.95;N,11.82.Found:C,64.25;H, 5.95;N,11.81.3-(2-(2-(2-Octanylidene)hydrazynyl)thiazol-4-yl)-2H-chro-men-2-one (9).Yellow crystals,74%yield,mp 149–150 C;1H NMR (DMSO-d 6):d 0.84–0.88(m,3H,CH 3),1.25–1.32(m,6H,3ÂCH 2),1.47–1.51(m,2H,CH 2),1.88–1.91(m,3H,CH 3),2.19–2.23(m,2H,CH 2),7.37–7.39(m,1H,C 7H-chrom.),7.42–7.44(m 1H,C 5H-chrom.),7.60–7.64(m,C 6H-chrom.),7.68(s,1H,C 5H-thiaz.),7.77–7.80(m,1H,C 8H-chrom.),8.53(s,1H,C 4H-chrom.),10.71(br s,1H,NH,D 2O exch.);Anal.Calcd.for C 20H 23N 3O 2S:C,65.01;H,6.27;N,11.37.Found:C,65.06;H,6.28;N,11.35.3-(2-(2-(2-Methylcyclopentylidene)hydrazynyl)thiazol-4-yl)-2H-chromen-2-one (10).Yellow crystals,79%yield,mp 143–145 C;1H NMR (CDCl 3):d 1.21–1.23(m,3H,CH 3),1.31–1.39(m,1H,cyclopentyl), 1.71–1.77(m,1H,cyclopentyl),1.95–2.02(m,1H,cyclopentyl),2.05–2.12(m,1H,cyclopen-tyl),2.25–2.33(m,1H,cyclopentyl),2.37–2.46(m,1H,cyclo-pentyl),2.58–2.64(m,1H,cyclopentyl),7.27–7.33(m,J 7-6¼J 7-8¼7.7Hz,J 7-5¼3.63Hz,1H,C 7H-chrom.),7.34–7.37(dd,J 5-6¼7.8,J 5-7¼3.6,1H,C 5H-chrom.),7.50–7.54(m,J 6-5¼J 6-7¼7.7Hz,J 6-8¼3.7Hz,1H,C 6H-chrom.),7.57–7.60(dd,J 8-7¼7.7,J 8-6¼3.6,1H,C 8H-chrom.),7.88(s,1H,C 5H-thiaz.),8.49(s,1H,C 4H-chrom.),12.00(br s,1H,NH,D 2O exch.);Anal.Calcd.for C 18H 17N 3O 2S:C,63.70;H,5.05;N,12.38.Found:C,63.75;H,5.04;N,12.39.3-(2-(2-(3-Methylcyclopentylidene)hydrazynyl)thiazol-4-yl)-2H-chromen-2-one (11).Light yellow crystals,99%yield,mp 214–216 C;1H NMR (CDCl 3):d 1.10–1.12(m,3H,CH 3),1.49–1.56(m,1H,cyclopentyl),2.10–2.12(m,1H,cyclopen-tyl),2.14–2.17(m,1H,cyclopentyl),2.19–2.22(m,1H,cyclo-pentyl), 2.54–2.62(m,1H,cyclopentyl), 2.64–2.73(m,1H,cyclopentyl), 2.75–2.81(m,1H,cyclopentyl),7.35–7.38(m,J 7-6¼J 7-8¼7.9Hz,J 7-5¼3.3Hz,1H,C 7H-chrom.),7.38–7.40(dd,J 5-6¼8.0,J 5-7¼3.2,1H,C 5H-chrom.),7.63–7.67(m,J 6-5¼J 6-7¼7.9Hz,J 6-8¼3.3Hz,1H,C 6H-chrom.),7.77–7.79(dd,J 8-7¼7.9,J 8-6¼3.4,1H,C 8H-chrom.),7.84(s,1H,C 5H-thiaz.),8.59(s,1H,C 4H-chrom.),11.80(br s,1H,NH,D 2O exch.);Anal.Calcd.for C 18H 17N 3O 2S:C,63.70;H,5.05;N,12.38.Found:C,63.65;H,5.06;N,12.38.3-(2-(2-(Cyclooctylidene)hydrazynyl)thiazol-4-yl)-2H-chro-men-2-one (12).Yellow crystals,69%yield,mp 143–145 C;1H NMR (CDCl 3):d 1.47–1.50(m,2H,cyclooctyl),1.52–1.58(m,4H,cyclooctyl),1.79–1.84(m,4H,cyclooctyl),2.43–2.46(m,4H,cyclooctyl),7.27–7.30(m,J 7-6¼J 7-8¼7.5Hz,J 7-5¼1.6Hz,1H,C 7H-chrom.),7.38–7.40(dd,J 5-6¼7.4,J 5-7¼1.7,1H,C 5H-chrom.),7.50–7.54(m,J 6-5¼J 6-7¼7.4Hz,J 6-8¼1.7Hz,1H,C 6H-chrom.),7.69–7.71(dd,J 8-7¼7.4,J 8-6¼1.7,1H,C 8H-chrom.),7.87(s,1H,C 5H-thiaz.),8.51(s,1H,C 4H-chrom.),11.97(br s,1H,NH,D 2O exch.);Anal.Calcd.for C 20H 21N 3O 2S:C,65.37;H, 5.76;N,11.44.Found:C,65.33;H,5.76;N,11.45.3-(2-(2-(1-(Cyclohexyl)ethyliden)hydrazynyl)thiazol-4-yl)-2H-chromen-2-one (13).Yellow crystals,69%yield,mp 195–200 C;1H NMR (DMSO-d 6):d 1.48–1.52(m,2H,cyclo-hexyl), 1.75–1.79(m,4H,cyclohexyl), 2.41–2.45(m,4H,cyclohexyl),7.37–7.41(m,J 7-6¼J 7-8¼7.5Hz,J 7-5¼1.8Hz,1H,C 7H-chrom.),7.41–7.43(dd,J 5-6¼7.6,J 5-7¼1.9,1H,C 5H-chrom.),7.53–7.57(m,J 6-5¼J 6-7¼7.5Hz,J 6-8¼1.8Hz,1H,C 6H-chrom.),7.68–7.70(dd,J 8-7¼7.9,J 8-6¼1.7,1H,C 8H-chrom.),7.85(s,1H,C 5H-thiaz.),8.54(s,1H,C 4H-chrom.),11.75(br s,1H,NH,D 2O exch.);Anal.Calcd.for C 20H 21N 3O 2S:C,65.37;H, 5.76;N,11.44.Found:C,65.33;H,5.77;N,11.45.3-(2-(2-(1-(Furan-2-yl)ethyliden)hydrazynyl)thiazol-4-yl)-2H-chromen-2-one (15).Light green crystals,77%yield,mp 218–220 C;1H NMR (DMSO-d 6):d 2.25(s,3H,CH 3),6.57–6.58(d,J 3-4¼1.7Hz,1H,C 3H-furan),6.84–6.86(dd,J 4-5¼3.3Hz,J 4-3¼1.7Hz,1H,C 4H-furan),7.37–7.41(m,J 7-6¼J 7-8¼7.6Hz,J 7-5¼2.9Hz,1H,C 7H-chrom.),7.44–7.47(dd,J 5-6¼7.6Hz,J 5-7¼2.6Hz,1H,C 5H-chrom.),7.61–7.63(m,J 6-5¼J 6-7¼7.2Hz,J 6-8¼2.9Hz,1H,C 6H-chrom.),7.73–7.75(d,J 5-4¼3.3Hz,1H,C 5H-furan),7.76(s,1H,C 5H-thiaz.),7.80–7.83(dd,J 8-7¼7.6Hz,J 8-6¼2.9Hz,1H,C 8H-chrom.),8.56(s,1H,C 4H-chrom.),11.25(br s,1H,NH,D 2O exch.);Anal.Calcd.for C 18H 13N 3O 3S:C,61.53;H,3.73;N,11.96.Found:C,61.56;H,3.72;N,11.98.3-(2-(2-(Thiophen-2-ylmethylen)hydrazynyl)thiazol-4-yl)-2H-chromen-2-one (16).Yellow crystals,99%yield,mp 230–235 C;1H NMR (DMSO-d 6):d 7.08–7.12(m,1H,thio-phene),7.37–7.40(m,1H,thiophene),7.41(s,1H,C 5H-thiaz.),7.43–7.48(m,J 7-6¼J 7-8¼6.8Hz,J 7-5¼3.4Hz,1H,C 7H-chrom.),7.58–7.62(dd,J 5-6¼6.3Hz,J 5-7¼3.3Hz,1H,C 5H-chrom.),7.63–7.68(m,1H,thiophene),7.75–7.78(m,1H,C 8H-chrom.),7.82–7.87(m,J 6-5¼J 6-7¼6.3Hz,J 6-8¼3.4Hz,1H,C 6H-chrom.),8.24(s,1H,CH ¼¼N),8.53(s,1H,C 4H-chrom.),12.10(br s,1H,NH,D 2O exch.);Anal.Calcd.for C 17H 11N 3O 2S 2:C,57.77;H,3.14;N,11.89.Found:C,57.72;H,3.15;N,11.90.3-(2-(2-(1-(Thiophen-2-yl)ethyliden)hydrazynyl)thiazol-4-yl)-2H-chromen-2-one (17).Yellow crystals,92%yield,mp 221–223 C;1H NMR (DMSO-d 6):d 2.31(s,3H,CH 3),7.03–7.06(m,1H,thiophene),7.37–7.40(m,1H,C 7H-chrom.),7.45–7.47(dd,J 5-6¼7.4Hz,J 5-7¼2.1Hz,1H,C 5H-chrom.),7.52–7.55(m,1H,thiophene),7.57–7.60(m,1H,thiophene),7.61–7.64(m,1H,C 6H-chrom.),7.77(s,1H,C 5H-thiaz.),7.81–7.84(dd,J 8-7¼7.4,J 8-6¼2.5,1H,C 8H-chrom.),8.57(s,1H,C 4H-chrom.),11.20(br s,1H,NH,D 2O exch.);Anal.Calcd.for C 17H 11N 3O 2S 2:C,57.61;H,3.41;N,11.86.Found:C,57.60;H,3.42;N,11.86.3-(2-(2-(1-(Pyridin-2-yl)ethyliden)hydrazynyl)thiazol-4-yl)-2H-chromen-2-one (19).Orange crystals,99%yield,mp 258–262 C;1H NMR (DMSO-d 6):d 2.41(s,3H,CH 3),7.37–7.40(m,1H,C 7H-chrom.),7.42–7.47(dd,J 5-6¼7.5Hz,J 5-7¼1.9Hz,1H,C 5H-chrom.),7.50–7.54(m,J 6-5¼J 6-7¼7.3Hz,J 6-8¼1.2Hz,1H,C 6H-chrom.),7.55–7.61(m,1H,C 5H-pyridine),7.81(s,1H,C 5H-thiaz.),7.82–7.84(dd,J 8-7¼7.3Hz,J 8-6¼1.3Hz,1H,C 8H-chrom.),8.05–8.10(m,1H,C 4H-pyridine),8.11–8.13(m,1H,C 3H-pyri-dine),8.58(s,1H,C 4H-chrom.),8.63–8.65(m,1H,C 6H-pyri-dine),11.77(br s,1H,NH,D 2O exch.);Anal.Calcd.for C 19H 14N 4O 2S:C,62.97;H,3.89;N,15.46.Found:C,62.95;H,3.88;N,15.45.S.Carradori,M.D’Ascenzio,M.Maddalena Scaltrito,and F.Sisto3-(2-(2-(1-(Pyridin-3-yl)methylen)hydrazynyl)thiazol-4-yl)-2H-chromen-2-one(20).Yellow crystals,99%yield,mp 257–258 C;1H NMR(DMSO-d6):7.32–7.35(m,1H,C7H-chrom.),7.38–7.41(dd,J5-6¼7.5Hz,J5-7¼1.3Hz,1H, C5H-chrom.),7.60–7.64(m,1H,C6H-chrom.),7.80–7.83(dd, J8-7¼7.6Hz,J8-6¼1.4Hz,1H,C8H-chrom.),7.84(s,1H, C5H-thiaz.),7.85–7.88(m,1H,C5H-pyridine),8.17(s,1H, CH¼¼N),8.48–8.52(m,1H,C4H-pyridine),8.56(s,1H,C4H-chrom.),8.73–8.75(m,1H,C6H-pyridine),9.01(s,1H,C2H-pyridine),12.75(br s,1H,NH,D2O exch.);Anal.Calcd.for C18H12N4O2S:C,62.06;H,3.47;N,16.08.Found:C,62.07; H,3.48;N,16.10.3-(2-(2-(1-(Pyridin-3-yl)ethyliden)hydrazynyl)thiazol-4-yl)-2H-chromen-2-one(21).Yellow crystals,99%yield,mp 269–270 C;1H NMR(DMSO-d6):d2.41(s,3H,CH3),7.40–7.44(m,1H,C7H-chrom.),7.48–7.50(dd,J5-6¼7.8Hz,J5-7¼1.7Hz,1H,C5H-chrom.),7.58–7.62(m,1H,C6H-chrom.), 7.80–7.83(dd,J8-7¼7.7Hz,J8-6¼1.7Hz,1H,C8H-chrom.),7.84(s,1H,C5H-thiaz.),7.87–7.90(m,1H,C5H-pyridine),8.52(s,1H,C4H-chrom.),8.55–8.58(m,1H,C4H-pyridine), 8.72–8.74(m,1H,C6H-pyridine),9.07(s,1H,C2H-pyridine), 11.75(br s,1H,NH,D2O exch.);Anal.Calcd.for C19H14N4O2S:C,62.97;H,3.89;N,15.46.Found:C,62.98; H,3.90;N,15.46.3-(2-(2-(1-(Pyridin-4-yl)methylen)hydrazynyl)thiazol-4-yl)-2H-chromen-2-one(22).Orange crystals,99%yield,mp> 300 C;1H NMR(DMSO-d6):7.40–7.43(m,1H,C7H-chrom.), 7.48–7.50(dd,J5-6¼7.9Hz,J5-7¼1.4Hz,1H,C5H-chrom.), 7.59–7.63(m,1H,C6H-chrom.),7.85–7.88(dd,J8-7¼7.6Hz, J8-6¼1.5Hz,1H,C8H-chrom.),7.91(s,1H,C5H-thiaz.), 8.07–8.10(d,J¼4.1Hz,2H,pyridine),8.16(s,1H,CH¼¼N), 8.55(s,1H,C4H-chrom.),8.81–8.83(d,J¼4.5Hz,2H,pyri-dine),13.00(br s,1H,NH,D2O exch.);Anal.Calcd.for C18H12N4O2S:C,62.06;H,3.47;N,16.08.Found:C,62.05; H,3.46;N,16.08.3-(2-(2-(1-(Pyridin-4-yl)ethyliden)hydrazynyl)thiazol-4-yl)-2H-chromen-2-one(23).Yellow crystals,98%yield,mp 215–220 C;1H NMR(DMSO-d6):d2.41(s,3H,CH3),7.42–7.46(m,1H,C7H-chrom.),7.48–7.50(dd,J5-6¼7.4Hz,J5-7¼1.6Hz,1H,C5H-chrom.),7.64–7.68(m,1H,C6H-chrom.), 7.76–7.78(dd,J8-7¼7.5Hz,J8-6¼1.9Hz,1H,C8H-chrom.), 7.85(s,1H,C5H-thiaz.),8.45–8.48(d,J¼5.8Hz,2H,pyri-dine),8.67(s,1H,C4H-chrom.),8.78–8.81(d,J¼5.8Hz, 2H,pyridine),10.75(br s,1H,NH,D2O exch.);Anal.Calcd. for C19H14N4O2S:C,62.97;H, 3.89;N,15.46.Found:C, 62.95;H,3.98;N,15.45.3-(2-(2-(1-(1H-indol-4-yl)methylen)hydrazynyl)thiazol-4-yl)-2H-chromen-2-one(24).Yellow crystals,90%yield,mp248–250 C;1H NMR(DMSO-d6):6.95–6.98(t,J¼3.5,1H,C5H-indole),7.12–7.15(t,J¼3.7,1H,C6H-indole),7.32(s,1H,C2H-indole),7.39–7.43(m,J7-6¼J7-8¼7.3Hz,J7-5¼1.7Hz,1H, C7H-chrom.),7.44–7.46(d,J¼3.7,1H,C7H-indole),7.48–7.50 (dd,J5-6¼7.3Hz,J5-7¼1.7Hz,1H,C5H-chrom.),7.49–7.53 (m,1H,C6H-chrom.),7.55(s,1H,C5H-thiaz.),7.58–7.60(dd,J8-7¼7.3Hz,J8-6¼1.3Hz,1H,C8H-chrom.),7.62–7.64(d,J¼3.5,1H,C4H-indole),8.16(s,1H,CH¼¼N),8.57(s,1H,C4H-chrom.),10.79(br s,1H,NH,D2O exch.),11.51(br s,1H,NH, D2O exch.);Anal.Calcd.for C21H14N4O2S:C,65.27;H,3.65;N, 14.50.Found:C,65.25;H,3.64;N,14.51.3-(2-(2-(1-(Naphthalen-1-yl)methylen)hydrazynyl)thiazol-4-yl)-2H-chromen-2-one(26).Yellow crystals,70%yield,mp 240–242 C;1H NMR(DMSO-d6):7.40–7.44(m,1H,C7H-chrom.),7.49–7.51(dd,J5-6¼7.8Hz,J5-7¼1.5Hz,1H, C5H-chrom.),7.53–7.55(m,1H,C6H-chrom.),7.56(s,1H, C5H-thiaz.),7.57–7.60(dd,J8-7¼7.8Hz,J8-6¼1.3Hz,1H, C8H-chrom.),7.77–7.81(m,2H,naphtalene),7.82–7.85(m, 1H,naphtalene),7.97–8.02(m,2H,naphtalene),8.08–8.10(m, 1H,naphtalene),8.12(s,1H,CH¼¼N),8.22–8.24(m,1H, naphtalene),8.60(s,1H,C4H-chrom.),11.54(br s,1H,NH, D2O exch.);Anal.Calcd.for C24H17N3O2S:C,70.05;H,4.16; N,10.21.Found:C,70.00;H,4.15;N,10.22.3-(2-(2-(1-(Naphthalen-2-yl)ethyliden)hydrazynyl)thiazol-4-yl)-2H-chromen-2-one(27).Yellow crystals,91%yield,mp 244–245 C;1H NMR(DMSO-d6):7.38–7.42(m,1H,C7H-chrom.),7.46–7.48(dd,J5-6¼7.4Hz,J5-7¼1.8Hz,1H, C5H-chrom.),7.49–7.53(m,1H,C6H-chrom.),7.54(s,1H, C5H-thiaz.),7.58–7.60(dd,J8-7¼7.3Hz,J8-6¼1.4Hz,1H, C8H-chrom.),7.77–7.82(m,2H,naphtalene),7.90–7.94(m, 2H,naphtalene),7.98–8.01(m,1H,naphtalene),8.08–8.10(m, 1H,naphtalene),8.21–8.23(m,1H,naphtalene),8.59(s,1H, C4H-chrom.),11.50(br s,1H,NH,D2O exch.);Anal.Calcd. for C24H17N3O2S:C,70.05;H, 4.16;N,10.21.Found:C, 70.00;H,4.15;N,10.22.9-(2-(4-(2H-2-oxo-chromen-3-yl)thiazol-2-yl)hydrazono)-9H-ﬂuorene-2-carboxylic acid(29).Yellow crystals,99%yield, mp190–192 C;1H NMR(DMSO-d6):7.28–7.30(m,1H,ﬂuo-rene),7.38–7.42(m,1H,C7H-chrom.),7.45–7.47(dd,J5-6¼7.7Hz,J5-7¼1.3Hz,1H,C5H-chrom.),7.49–7.53(m,1H, C6H-chrom.),7.56(s,1H,C5H-thiaz.),7.57–7.61(m,2H,ﬂuo-rene),7.62–7.64(dd,J8-7¼7.4Hz,J8-6¼1.4Hz,1H,C8H-chrom.),7.78–7.82(m,2H,ﬂuorene),8.33–8.38(m,2H,ﬂuo-rene),8.57(s,1H,C4H-chrom.),11.77(br s,1H,COOH,D2O exch.),12.50(br s,1H,NH,D2O exch.);Anal.Calcd.for C26H15N3O4S:C,67.09;H,3.25;N,9.03.Found:C,67.13;H, 3.25;N,9.04.3-(2-(2-(1-(Thiazol-2-yl)ethyliden)hydrazynyl)thiazol-4-yl)-2H-chromen-2-one(30).Light brown crystals,99%yield,mp 256–260 C;1H NMR(DMSO-d6):d2.43(s,3H,CH3),7.39–7.43(m,1H,C7H-chrom.),7.46–7.48(dd,J5-6¼8.0Hz,J5-7¼1.6Hz,1H,C5H-chrom.),7.63–7.67(m,1H,C6H-chrom.), 7.79(s,1H,C5H-thiaz.),7.83–7.85(dd,J8-7¼7.9Hz,J8-6¼1.8Hz,1H,C8H-chrom.),7.86–7.89(m,2H,thiazole),8.72(s, 1H,C4H-chrom.),11.75(br s,1H,NH,D2O exch.);Anal. Calcd.for C17H12N4O2S2:C,55.42;H,3.28;N,15.21.Found: C,55.47;H,3.28;N,15.24.Procedure for the synthesis of derivative31.3-a-Bromo-acetyl coumarin(50mmol)was dissolved in2-propanol and reacted with an equimolar amount of thiosemicarbazide at room temperature under magnetic stirring for4h.The precipi-tate wasﬁltered and dried to give intermediate31.H.pylori culture.The H.pylori strains used in this study were maintained atÀ80 C in Wilkins Chalgren broth with 10%(v/v)horse serum(Seromed)and20%(v/v)glycerol (Merck)until required for the experiments.Before being used the bacteria were subcultured twice on Columbia agar base (Difco Laboratories)supplemented with10%horse serum and 0.25%Bacto yeast extract(Difco).Plates were incubated for 72h at37 C in an atmosphere of10%CO2in a gas incubator. Anti-Helicobacter pylori activity.Antimicrobial activity against H.pylori was determined by the agar dilution standard method[19].The strains were inoculated onto Columbia agar base(Difco)supplemented with10%horse serum and0.25%4-(Coumarin-3-yl)thiazol-2-ylhydrazone Derivativesbacto yeast extract(Difco)and were incubated for72h at 37 C in an atmosphere of10%CO2in a gas incubator.Colo-nies were suspended in Wilkins Chalgren broth to achieve a turbidity equivalent to0.5Mc Farland.Columbia agar plates with10%horse serum were prepared by using twofold dilu-tions of the antimicrobial agents(128–0.0039l g/mL).The inoculum was delivered to the surface of the agar plates with a Steer’s replicator to obtain$5Â105CFU per spot.Growth control plates without antibiotics were inoculated in each se-ries of tests.All plates were incubated at37 C for72h under conditions(10%CO2in a gas incubator).The minimal inhibi-tory concentration was deﬁned as the lowest concentration of drug inhibiting visible bacterial growth.REFERENCES AND NOTES[1]Hunt,R.H.Scand J Gastroenterol1996,220,3.[2]Bardhan,P.K.Clin Infect Dis1997,25,973.[3]IARC.IARC monographs on the evaluation of carcinogenic risks to humans,Vol.61;IARC:Lyon,1994;pp177–240.[4]Chimenti,F.;Bizzarri,B.;Bolasco,A.;Secci,D.;Chimenti, P.;Carradori,S.;Granese,A.;Rivanera,D.;Lilli,D.;Scaltrito,M.M.; Brenciaglia,M.I.Eur J Med Chem2006,41,208.[5]Chimenti,F.;Bizzarri,B.;Bolasco,A.;Secci,D.;Chimenti, P.;Carradori,S.;Granese,A.;Rivanera,D.;Lilli,D.;Zicari,A.;Scal-trito,M.M.;Sisto,F.Bioorg Med Chem Lett2007,17,3065.[6]Kawase,M.;Motohashi,N.Curr Med Chem Anti-Infect Agents2004,3,89.[7]Chimenti, F.;Carradori,S.;Secci, D.;Bolasco, A.;Chi-menti,P.;Granese,A.;Bizzarri,B.J Heterocycl Chem2009,46,575.[8]Raghu,M.;Nagaraj,A.;Reddy,Ch.S.J Heterocycl Chem 2009,46,261.[9]Rao,V.R.;Reddy,M.M.M.Indian J Heterocycl Chem 2003,13,69.[10]Kalluraya,B.;Isloor,A.M.;Shenoy,S.Indian J Heterocycl Chem2001,11,159.[11]Kalluraya, B.;Vishwanatha,P.;Isloor, A.M.;Rai,G.; Kotian,M.Bollettino Chimico Farmaceutico2000,139,263.[12]Rao,V.R.;Kumar,V.R.;Vardhan,V.A.Phosphorus Sul-fur1999,152,257.[13]Srimanth,K.;Rao,V.R.Indian J Chem B1999,38B,473.[14]Gursoy,A.J Fac Pharm Istanbul U1974,10,57.[15]Gursoy,A.;Eczacilik F.J Fac Pharm Istanbul U1973,9, 51.[16]Rao,V.R.;Srimanth,K.J Chem Res S2002,9,420.[17]Benassi,R.;Benedetti, A.;Taddei, F.;Cappelletti,R.; Nardi,D.;Tajana, Magn Reson1982,20,26.[18]Cirilli,R.;Ferretti,R.;La Torre,F.;Secci,D.;Bolasco,A.; Carradori,S.;Pierini,M.J Chromatogr A2007,1172,160.[19]National Committee for Clinical Laboratory Standards. Methods for Antimicrobial Susceptibility Testing of Anaerobic bacte-ria.Approved standard M11-A6,6th ed.;National Committee for Clin-ical Laboratory Standards:Villanova,PA,2004.S.Carradori,M.D’Ascenzio,M.Maddalena Scaltrito,and F.Sisto。

4-异丁基苯基-4'-甲基苯基碘鎓六氟磷酸盐

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文档下载后可定制随意修改，请根据实际需要进行相应的调整和使用，谢谢!并且，本店铺为大家提供各种各样类型的实用资料，如教育随笔、日记赏析、句子摘抄、古诗大全、经典美文、话题作文、工作总结、词语解析、文案摘录、其他资料等等，如想了解不同资料格式和写法，敬请关注!Download tips: This document is carefully compiled by theeditor.I hope that after you download them,they can help yousolve practical problems. The document can be customized andmodified after downloading,please adjust and use it according toactual needs, thank you!In addition, our shop provides you with various types ofpractical materials,such as educational essays, diaryappreciation,sentence excerpts,ancient poems,classic articles,topic composition,work summary,word parsing,copy excerpts,other materials and so on,want to know different data formats andwriting methods,please pay attention!4-异丁基苯基-4'-甲基苯基碘鎓六氟磷酸盐：一种重要的有机化学试剂4-异丁基苯基-4'-甲基苯基碘鎓六氟磷酸盐，是一种在有机合成化学中广泛应用的卤素离子试剂，其化学式为(C6H4(CH3)(C4H9)I)[PF6]。

马丁斯蒂克洛比4蒸发性净化剂说明书

1. IDENTIFICATIONPRODUCT NAME: Martin’s Triclopyr 4 DESCRIPTION: A liquid herbicide. EPA Reg. No.: 81927-11-53883 COMPANY IDENTIFICATION: Control Solutions, Inc. 5903 Genoa Red Bluff Pasadena, TX 775072. HAZARD IDENTIFICATIONDANGERMay be fatal if swallowed and enters airways (H304) Harmful if swallowed (H302)Causes mild skin irritation (H316)May cause an allergic skin reaction (H317) Very toxic to aquatic life (H400) Combustible liquid (H227)HAZARD CLASSIFICATIONHealth Hazard CategoryPhysical Hazards CategoryAspiration Hazard 1 Flammable Liquids 4 Sensitization, Skin1Skin Corrosion/Irritation 2B Environmental HazardsCategoryAcute Toxicity, Oral4 Hazardous to the aquatic environment, short-term 1PRECAUTIONARY STATEMENTSWash hands thoroughly after handling. Do not eat, drink or smoke when using this product. (P264+P270) Avoid breathing mist/vapors/spray. Contaminated work clothing should not be allowed out of the workplace. Wear protective gloves. (P261+P272+P280)Keep away from heat, hot surfaces, sparks, open flames and other ignition sources. No smoking. Wear protective gloves / protective clothing / eye protection / face protection. (P210+ + P273)Avoid release to the environment not in accordance with the product label. (P273)IF SWALLOWED: Immediately call a Poison Control Center of doctor. Rinse mouth. Do NOT induce vomiting. (P301+ P310+ P330+P331) IF ON SKIN: Wash with plenty of water. If skin irritation or rash occurs: Get medical advice or attention. Specific treatment (See Section 4 for additional medical information). Take off immediately all contaminated clothing. (P302+P352+ P333+313+P321+P362+P364) Collect spillage. (P391) Store locked up. (P405)Dispose of contents / containers in accordance with local, State and Federal regulations. Refer to the product label for specific disposal instructions. (P501)3. COMPOSITION / INFORMATION ON INGREDIENTSCommon NameChemical NameCAS #CompositionTriclopyr BEE(3,5,6-trichloro-2-pyridinyl)oxyacetic acid, butoxyethyl ester 64700-56-7 61.6% Aromatic HydrocarbonsSolvent Naphtha (Petroleum), Heavy Aromatic64742-94-5> 25.0%4. FIRST AID MEASURESHave the product container or label with you when calling a poison control center or doctor or going for treatment. You may also contact CHEMTREC at 1-800-424-9300 for emergency medical treatment information.IF SWALLOWED: Call a poison control center or doctor immediately for treatment advice. Do not induce vomiting unless told to do so by the poison control center or doctor. Do not give anything by mouth to an unconscious person. Do not give liquid to the person.IF IN EYES: Hold eye open and rinse slowly and gently with water for 15-20 minutes. Remove contact lenses, if present, after the first 5 minutes, then continue rinsing eye. If eye irritation persists: Get medical advice/attention.IF ON SKIN OR CLOTHING: Take off contaminated clothing. Rinse skin immediately with plenty of water for 15-20 minutes. If skin irritation or rash occurs: Get medical advice / attention.NOTE TO PHYSICIAN: May pose aspiration hazard. Contains petroleum distillates.5. FIREFIGHTING MEASURESFire and Explosion Hazards: Thermal decomposition may release irritating gases and fumes (see Section 10).Extinguishing Medium: Foam, dry chemical, CO2 or water fog.Fire Fighting Equipment: Firefighters should be equipped with self-contained positive pressure breathing apparatus and full bunker gear.Fire Fighting Instructions: Evacuate area and fight fire upwind from a safe distance to avoid possible hazardous fumes and decomposition products. Dike runoff and do not allow runoff to enter sewers, storm drains or waterways. Foam and dry chemical extinguishing systems are preferred to prevent environmental damage from excessive water runoff.Hazardous Combustion Products: Hydrogen chloride, oxides of nitrogen, phosgene.NFPA Ratings: Health – 2 / Flammability – 2 / Reactivity - 06. ACCIDENTAL RELEASE MEASURESClean up spills immediately observing the precautions in Section 8 of this MSDS. Isolate the hazard area and keep unnecessary and unprotected personnel from entering. Prevent material from contaminating soil or from entering sewage and drainage systems and bodies of water.SMALL SPILLS: Absorb spill with sand, vermiculite or other inert absorbent. Place contaminated material into an appropriate container for disposal.LARGE SPILLS: Dike large spills using absorbent or impervious materials such as clay or sand. Recover and contain as much free liquid as possible for reuse. Allow absorbed material to solidify, scrape up and place in an appropriate container for disposal. After removal, flush contaminated area thoroughly with water, observing all environmental regulations. Recover wash liquid with additional absorbent and place in container for disposal.7. HANDLING AND STORAGEAvoid contact with skin, eyes and clothing. Wash hands before eating, drinking, chewing gum, using tobacco, or using the toilet. Remove clothing immediately if pesticide gets inside. Then wash thoroughly and put on clean clothing. Remove PPE immediately after handling this product. Wash the outside of gloves before removing. As soon as possible, wash thoroughly and change into clean clothing.Do not use or store near heat or open flame. Do not cut or weld container. Store above 28°F in a cool, dry place and in such a manner as to prevent cross contamination with other pesticides, fertilizers, food, and feed. Store in original container and out of the reach of children, preferably in a secured storage area.8. EXPOSURE CONTROLS / PERSONAL PROTECTIONEngineering Controls: Facilities storing or utilizing this material should be equipped with an eyewash station and a safety shower. Proper ventilation is required when handling or using this product to keep exposure to airborne contaminants below exposure limits. Local mechanical exhaust ventilation may be required.Protective Clothing: Long-sleeved shirt, long pants and shoes plus socks, and chemical resistant gloves (> 14 mils) such as butyl rubber, natural rubber, neoprene rubber, or nitrile rubber.General: Wash thoroughly with soap and water after handling. Discard clothing and other absorbent materials that have been heavily contaminated with this product; do not reuse them. Follow the manufacturer’s instructions for cleaning and maintaining PPE. If no such instructions for washables exist, use detergent and hot water. Keep and wash PPE separately from other laundry.9. PHYSICAL AND CHEMICAL PROPERTIESAppearance: Amber liquid Odor:Aromatic Solvent Melting/freezing point:not available Boiling point/Boiling range:not available Flammability:not available Flammability limits (upper/lower):not available Flash point:61.8°C (143.2°F) Auto-ignition temperature:not available Decomposition temperature:not available pH: 4.0 – 5.0 Kinematic viscosity:not available Solubility:Emulsifies Partition coefficient:not available Vapor pressure:not available Density: 1.075 g/mL (8.97 lbs/galRelative vapor density:not available Particle characteristics:not available10. STABILITY AND REACTIVITYCONDITIONS TO AVOID: Temperatures above40°C (105°F) and below -2°C (28°F).CHEMICAL STABILITY: Stable under all normal use and storage conditions. May thermally decompose. HAZARDOUS DECOMPOSITION PRODUCTS: Thermal decomposition may generate hydrogen chloride, oxides of nitrogen and phosgene.INCOMPATIBILITY WITH OTHER MATERIALS: Strong acids and oxidizing agents. POLYMERIZATION: Will not occur.11. TOXICOLOGICAL INFORMATIONORAL TOXICITY (rat LD50): > 1,000 mg/kgDERMAL TOXICITY (rabbit LD50): > 2,000 mg/kgINHALATION TOXICITY (rat LC50): > 5.2 mg/LEYE IRRITATION: Mildly irritatingSKIN IRRITATION: Moderately irritatingSKIN SENSITIZATION: Potential sensitizer after repeated exposures to concentrate. CARCINOGENICITY:EPA:Not listed.ACGIH: Not Listed NTP:Not ListedIARC:Not Listed OSHA: Not ListedMUTAGENIC TOXICITY: Little evidence of mutagenic effects during in vivo and in vitro assays. REPRODUCTIVE TOXICITY: No evidence in animal studies.12. ECOLOGICAL INFORMATIONThis pesticide is toxic to fish. Do not apply directly to water, to areas where surface water is present, or to intertidal areas below the mean high water mark. Do not contaminate water when cleaning equipment or disposing of equipment washwaters or rinsate.This herbicide is injurious to plants at extremely low concentrations. Nontarget plants may be adversely affected from drift and run-off.This chemical has properties and characteristics associated with chemicals detected in groundwater. The use of this chemical in areas where soils are permeable, particularly where the water table is shallow, may result in groundwater contamination.AQUATIC TOXICITY TERRESTRIAL TOXICITYBluegill sunfish 96-hr LC50: 0.44 mg/L Bobwhite quail oral LD50: 1350 mg/kg Daphnia magna 48-hr EC50: 0.35 mg/L Honeybee contact and oral LD50: >230 µg/bee Green Algae E b C50: 10.6 mg/L13. DISPOSAL CONSIDERATIONSPESTICIDE DISPOSAL: Do not contaminate water, food or feed by disposal.Wastes resulting from the use of this product (that cannot be used according to label instructions) must be disposed of on site or at an approved waste disposal facility.CONTAINER DISPOSAL: Refer to the product label for specific container handling instructions.14. TRANSPORT INFORMATIONUN Number: UN3082Proper Shipping Name: Environmentally hazardous substance, liquid, N.O.S. (contains Triclopyr,Aromatic Hydrocarbons)Transport Hazard Class: 9Packing Group: IIIHazard Zone: AMarine Pollutant: Yes1Hazardous Substance RQ: NoneLabels / Placards: US-DOT: Combustible Liquid2IMDG, IATA: Class 9 Environmentally Hazardous Substance3 Emergency Guide: 171 (NAERG – North American Emergency Response Guide)1 Marine Pollutant Note: Ground-only shipments are excluded from Marine Pollutant labelingrequirements as per 49 CFR 172.101 Appendix B (4). For any shipmentsinvolving all or part of the transport by vessel, the shipment must beclassified as a Marine Pollutant unless a limited quantity exemptionapplies (see note 3 below).2 US-DOT Note: Containers < 119 Gallons shipped by land or vessel not regulated fordomestic transport. Containers ≥ 119 gallons o r shipments by air must beshipped as NA1993, Combustible Liquid, N.O.S. (contains Triclopyr,Aromatic Hydrocarbons), PG III. Emergency response guide 128.3 IMDG / IATA Note: Not regulated when shipped in single or inner packaging ≤ 1.3 gallons (5liters)This information is not intended to convey all specific regulatory or operational requirements/information relating to this product. Transportation classifications may vary by container volume and may be influenced by regional or country variations in regulations. Additional transportation system information can be obtained through an authorized sales or customer service representative. It is the responsibility of the transporting organization to follow all applicable laws, regulations and rules relating to the transportation of the material.15. REGULATORY INFORMATIONFIFRA –This chemical is a pesticide product registered by the Environmental Protection Agency and is subject to certain labeling requirements under federal pesticide law. These requirements differ from the classification criteria and hazard information required for safety data sheets, and for workplace labels of non-pesticide chemicals. The following is the hazard information as required on the pesticide label: PRECAUTIONARY STATEMENTSHAZARDS TO HUMANS AND DOMESTIC ANIMALSCAUTION: Harmful if swallowed. Causes moderate eye irritation. Avoid contact with eyes orclothing. Prolonged or frequently repeated skin contact may cause allergic reactions in someindividuals.ENVIRONMENTAL HAZARDSThis pesticide is toxic to fish. Do not apply directly to water, to areas where surface water ispresent, or to intertidal areas below the mean high water mark. Do not contaminate waterwhen cleaning equipment or disposing of equipment washwaters or rinsate.This chemical has properties and characteristics associated with chemicals detected ingroundwater. The use of this chemical in areas where soils are permeable, particularly wherethe water table is shallow, may result in groundwater contamination.Physical or Chemical HazardsCombustible: Do not use or store near heat or open flame. Do not cut or weld container.All pesticides are governed under the Federal Insecticide, Fungicide, and Rodenticide Act (FIFRA). The regulatory information presented below is pertinent only when this product is handled outside of the normal use and application as a pesticide. This product is excluded from listing requirements under EPA/TSCA. SARA Title III – Section 302 Extremely Hazardous SubstancesNot listedSARA Title III – Section 311/312 Hazard CategoriesImmediate, Delayed, FireSARA Title III – Section 312 Threshold Planning QuantityThe threshold planning quantity (TPQ) for this product treated as a mixture is 10,000 lbs. This product contains no ingredients with a TPQ of less than 10,000 lbs.SARA Title III – Section 313 Reportable IngredientsNoneCERCLA –N/ACALIFORNIA PROP 65 STATUS –This product does not contain any products known to the state of California to cause cancer or reproductive harm.CANADA –This product has been classified in accordance with the hazard criteria of the Controlled Products Regulations (CPR) and the SDS contains all of the information required by CPR.16. OTHER INFORMATIONThis Safety Data Sheet (SDS) serves different purposes than and DOES NOT REPLACE OR MODIFY THE EPA APPROVED PRODUCT LABELING (attached to and accompanying the product container). This SDS provides important health, safety, and environmental information for employers, employees, emergency responders and others handling large quantities of the product in activities generally other than product use, while the labeling provides that information specifically for product use in the ordinary course.To the extent consistent with applicable law, neither Control Solutions, Inc. nor Seller be liable for any indirect, special, incidental or consequential damages resulting from the use, handling, application, storage, or disposal of this product. To the extent consistent with applicable law, the exclusive remedy of the user or buyer for any and all losses, injuries or damages resulting from the use, handling, application, or storage of this product, whether in contract, warranty, tort, negligence, strict liability or otherwise, shall not exceed the purchase price paid.SDS Version: 3.0 Effective Date: 07/10/2018。

植物保护剂[发明专利]

专利名称：植物保护剂
专利类型：发明专利
发明人：安德列斯·柴可,拉兹劳·帕波,拉约斯·耐奇,埃瓦·索姆菲,基约奇·朱塞尼,伊斯特万·柴克里,阿尼考·代阿克,
阿哥尼斯·哈杰迪斯
申请号：CN89102068.3
申请日：19890407
公开号：CN1037821A
公开日：
19891213
专利内容由知识产权出版社提供
摘要：本发明是关于ULV植物保护杀节肢动物制剂，其中除了含有溶解在脂肪烃和向日葵油混合物中的添加剂外还含有烷芳基聚乙二醇醚。

本发明制剂对植物表面的初接触角大于13°，20分钟后大于6°， 120分钟后至少仍为2°。

申请人：奇诺英药物化学工厂有限公司
地址：匈牙利布达佩斯
国籍：HU
代理机构：中国国际贸易促进委员会专利代理部
代理人：张元忠
更多信息请下载全文后查看。

白木香肉桂酸—4—羟基化酶(C4H)基因的克隆及表达分析

白木香肉桂酸—4—羟基化酶（C4H）基因的克隆及表达分析标签：C4H酶；白木香；芳香族化合物；伤害国产沉香为瑞香科植物白木香Aquilaria sinensis（Lour. ）Gilg 含树脂的木材。

作为我国传统中药，沉香有具行气止痛、温中止呕、纳气平喘的功效，用于胸腹胀闷疼痛、胃寒呕吐呃逆、肾虚气逆喘急[1]。

沉香只有在健康白木香树受到外界伤害后才能形成[2]。

但是，伤害诱导沉香形成的分子机制一直未得到清晰揭示，制约了高效结香技术的建立。

沉香的化学成分主要为：倍半萜类、芳香族类成分和2-（2-苯乙基）色酮[3-4]。

合成芳香族化合物的苯丙烷途径的关键酶之一是肉桂酸-4-羟基化酶[5]。

研究表明，C4H在转录水平上的丰度和蛋白质水平上的活性能有效影响植物中芳香族化合物和黄酮类化合物的生物合成量[6-8]。

本实验根据已知的植物C4H的氨基酸序列进行同源序列比对，设计引物，应用RT-PCR从白木香中克隆C4H基因全长并进行序列分析，了解白木香C4H 基因的结构与功能，这对从分子水平上探讨白木香苯丙烷类次生代谢途径具有重要意义。

1 材料中国医学科学院药用植物研究所温室栽培的3年生白木香茎诱导产生的愈伤分别进行机械伤害（用灭菌后的刀片切割至体积约为5 mm3的小块）和100 μmol·L-1 MeJA（茉莉酸甲酯）处理，于处理后2，4，8，12，16，20，24 h取样，用于提取总RNA，检测C4H基因在健康和伤害后愈伤组织中的表达差异。

2 方法2.1 总RNA提取按照EASYspin Plus植物RNA快速提取试剂盒（Aidlab，中国）实验操作步骤进行RNA制备，制备好的总RNA最终溶解于30 μL RNase free水中，1% 琼脂糖凝胶电泳检测RNA完整性，分光光度计NanoDrop 2000C （Thermo Scientific，美国）测定RNA浓度。

2.2 cDNA第一链的合成利用TaKaRa公司的M-MLV RTase cDNA Synthesis Kit 试剂盒将白木香总RNA反转录为第一链互补链DNA （cDNA）。

护发用新原料系列(三)植物油脂取代硅油

护发用新原料系列(三)植物油脂取代硅油
佚名
【期刊名称】《中国洗涤用品工业》
【年(卷),期】2004(000)005
【摘要】@@ 硅油广泛应用作为头发和皮肤类化妆品的光泽剂.近年来,"返璞归真,回归自然"已成为消费者的一大购物理念.用天然植物油脂取代硅油也成为重要的研究课题.为此,美国ZENITECH公司开发了ZENIGLOSS系列产品.
【总页数】1页(P38)
【正文语种】中文
【中图分类】TQ65
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4.几种植物油脂护发作用研究 [J], 周礼云; 万岳鹏; 龚盛昭; 李强
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