CN1654464A - N,N'-disubstituted dihydrazides compound and its preparing process and application thereof - Google Patents
N,N'-disubstituted dihydrazides compound and its preparing process and application thereof Download PDFInfo
- Publication number
- CN1654464A CN1654464A CN 200510013135 CN200510013135A CN1654464A CN 1654464 A CN1654464 A CN 1654464A CN 200510013135 CN200510013135 CN 200510013135 CN 200510013135 A CN200510013135 A CN 200510013135A CN 1654464 A CN1654464 A CN 1654464A
- Authority
- CN
- China
- Prior art keywords
- compound
- carbon
- mole
- gets
- alkyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Abstract
The present invention relates to N-5-chlorophenyl dihydropyran-6-formyl-N', N'-disubstituent dihydrazide compound and its preparation process, application and important intermediate preparing process. The compound has general expression as shown in I. The compound has excellent pesticidal activity, may be used widely in pest prevention and killing, and is one kind of pest growth regulator with wide application foreground.
Description
Technical field
The present invention relates to N; N '-two replaces two hydrazide kind compounds and preparation method and application; it is N-5-chlorobenzene and dihydropyrane-6-formyl radical-N ', and N '-two replaces two hydrazide kind compounds and preparation method and application, and the important intermediate preparation method of this compounds.
Background technology
EP-228564, EP-236618 and EP-245950 disclose N, N '-two hydrazide kind compound and insecticidal activity thereof, JP8231528, JP8231529, JP 4235177, US5482962 discloses and has contained benzo five-membered heterocyclic two hydrazide derivatives and insecticidal activity thereof, EP496342, EP984009 discloses two hydrazide derivatives and the insecticidal activity thereof that contains the benzo hexa-member heterocycle, and CN1313276 discloses two hydrazide derivatives and the insecticidal activity thereof that contains benzo five-membered heterocycle and benzo hexa-member heterocycle.
Summary of the invention
The purpose of this invention is to provide a kind of N; N '-two replaces two hydrazide kind compounds and preparation method and application; it is N-5-chlorobenzene and dihydropyrane-6-formyl radical-N '; N '-two replaces two hydrazide kind compounds and preparation method and application; this compounds has excellent insecticidal activity; can be widely used in the pest control of farm crop, be a kind of insect growth regulator(IGR) with broad prospect of application.
The present invention is to provide N-5-chlorobenzene and the dihydropyrane-6-formyl radical-N ' of chemical general formula for (I), N '-two replaces two hydrazide kind compounds, and it has structure shown in the following general formula (I):
Wherein, in the general formula (I), R
1Represent 1-6 carbon alkyl, 1-6 halocarbon substituted alkyl, 1-6 carbon alkoxyalkyl, 3-6 carbene base, 3-6 halo carbene base, 3-6 carbyne base, 3-7 carbocyclic ring alkyl or 3-6 carbon alkyl; R
2Represent phenyl, pyridyl, naphthyl, chroman, 2,3-dihydro-1,4-Ben Bing dioxazine, 4H-1,3-Ben Bing dioxazine, 2,3-dihydro-cumarone, cumarone, benzothiazole, 1,3-benzoxazole, 1,2-benzoisoxazole, benzoglyoxaline, each group is unsubstituted; Or replaced by one or more following radicals: halogen, 1-4 carbon alkyl, 1-4 carbon alkoxyl group, 1-4 halocarbon substituted alkyl, 1-4 halocarbon are for alkoxyl group, 1-4 carbon alkoxyalkyl, 1-4 carbon alkylthio, 1-4 carbon alkyl sulphinyl, 1-4 carbon alkyl sulphonyl, nitro, cyano group, hydroxyl, carboxyl, 1-4 carbon alkyl-carbonyl or 1-4 carbon alkoxy carbonyl.
Described two replace two hydrazide kind compounds is selected from:
R
1Represent 1-4 carbon alkyl; R
2Represent phenyl, pyridyl, naphthyl, chroman, 2,3-dihydro-1,4-Ben Bing dioxazine, 4H-1,3-Ben Bing dioxazine, 2,3-dihydro-cumarone, cumarone, benzothiazole, 1,3-benzoxazole, 1,2-benzoisoxazole, benzoglyoxaline, each group is unsubstituted; Or replaced by one or more following radicals: halogen, 1-4 carbon alkyl, 1-4 carbon alkoxyl group, 1-4 halocarbon substituted alkyl, 1-4 halocarbon are for alkoxyl group, 1-4 carbon alkoxyalkyl, 1-4 carbon alkylthio, 1-4 carbon alkyl sulphinyl, 1-4 carbon alkyl sulphonyl, nitro, cyano group, hydroxyl, carboxyl, 1-4 carbon alkyl-carbonyl or 1-4 carbon alkoxy carbonyl.
Described two replace two hydrazide kind compounds is selected from: R
1Represent 1-4 carbon alkyl, R
2Represent phenyl, pyridyl, chroman, or each group is replaced by one or more following radicals: halogen, 1-4 carbon alkyl, 1-4 carbon alkoxyl group, 1-4 halocarbon substituted alkyl, nitro.
Described two synthetic intermediates that replace two hydrazide kind compound I have structure shown in the following general formula I I:
Among the general formula I I, R
1Have and give definition in the claim 1.
The synthetic intermediate of described Compound I I has structure shown in following (III):
Two preparation methods that replace two hydrazide kind compounds of general formula I of the present invention are by following synthetic route preparation:
Compound 5-chlorobenzene and dihydropyrane-6-formic acid III and excessive oxalyl chloride room temperature reaction in methylene dichloride, or reflux with excessive thionyl chloride, excessive oxalyl chloride is sloughed in decompression or thionyl chloride makes 5-chlorobenzene and dihydropyrane-6-formyl chloride IV, need not to be further purified, with compound V under the alkali lye effect, reaction obtains II, and Compound I I makes N-5-chlorobenzene and dihydropyrane-6-formyl radical-N ' with the compound VI reaction in the presence of acid binding agent, and N '-two replaces two hydrazides class chemical combination I; R in the formula
1, R
2Have and give definition in the claim 1.
Oxalyl chloride that described compound 5-chlorobenzene and dihydropyrane-6-carboxylic acid III and 1.5-3.5 mole are doubly measured or thionyl chloride reaction make 5-chlorobenzene and dihydropyrane-6-formyl chloride IV; the hydrochloride reaction of the compound V that compound IV is doubly measured with the 1.5-2.5 mole in the presence of the sodium hydroxide that the 3-6 mole is doubly measured obtains Compound I I; the compound VI reaction that Compound I I doubly measures with the 1-1.2 mole in the presence of the acid binding agent triethylamine that the 1.2-1.5 mole is doubly measured makes N-5-chlorobenzene and dihydropyrane 6-formyl radical-N ', and N '-two replaces two hydrazide kind compound I.
The preparation method of described compound III prepares by following synthetic route:
Compound a and propargyl bromide react in toluene under sodium hydroxide solution and the effect of phase-transfer catalyst tetra-n-butyl ammonium bromide and make compound b, compound b is in N, the heating cyclization obtains compound c in the N-Diethyl Aniline, compound c gets compound d through palladium carbon catalytic hydrogenation, compound d gets Verbindung through the sulfuryl chloride chlorination, Verbindung aqueous acetic acid oxidation through chromic oxide in acetic acid gets compound f, compound f is in methylene dichloride, take off the tertiary butyl through aluminum chloride and get compound g, compound g gets compound III through the silver suboxide oxidation.
The 1-propargyl bromide that described compound a and 1.2-1.5 mole are doubly measured aqueous sodium hydroxide solution that the 1.2-1.5 mole is doubly measured and 0.01 mole doubly under the tetra-n-butyl ammonium bromide effect of amount in toluene reaction make compound b, the N that compound b is doubly measured in the 1.2-1.5 mole, the heating cyclization obtains compound c in the N-Diethyl Aniline, compound c gets compound d through the palladium carbon catalytic hydrogenation of catalytic amount, the sulfuryl chloride chlorination that compound d is doubly measured through the 1.0-1.2 mole gets Verbindung, the aqueous acetic acid oxidation of the chromic oxide that Verbindung is doubly measured through the 3-3.5 mole in acetic acid gets compound f, compound f is in methylene dichloride, the aluminum chloride of doubly measuring through the 2-2.5 mole takes off the tertiary butyl and gets compound g, and the silver suboxide oxidation that compound g doubly measures through the 1-1.2 mole gets compound III.
The compound of general formula of the present invention (I) has excellent insecticidal activity, can be used to prevent and treat the lepidopteran class, stick up wing order class, Heteroptera class, Diptera class, Orthoptera class and Homoptera class pest, is particularly suitable for preventing and treating the lepidopteran class pest.
The compound of general formula of the present invention (I) can directly use, and can add that also the carrier that agricultural go up to be accepted uses, also can with other sterilants and (or) the composite use of miticide.
Embodiment
Further specify the present invention below in conjunction with embodiment:
Embodiment 1:
Present embodiment explanation compound N '-tertiary butyl-N '-benzoyl-N-5-chlorobenzene and dihydropyrane-6-formyl hydrazine (compound 1) synthetic
With 150mg (0.53mmol) N '-tertiary butyl-N-5-chlorobenzene and dihydropyrane-6-formyl hydrazine (Compound I I, R
1=the tertiary butyl) and 64mg (0.64mmol) triethylamine be dissolved in the 5mL methylene dichloride, ice bath cooling drips methylene dichloride (1mL) solution of 74.5mg (0.53mmol) Benzoyl chloride down, drips and finishes, stirring at room 3h adds the dilution of 50mL ethyl acetate, tells organic layer, water, saturated brine washing successively, anhydrous sodium sulfate drying, the decompression precipitation gets white solid, get clear crystal 156.1mg through the Virahol recrystallization, yield: 76.2%, mp:247-248 ℃
1H NMR δ: 1.60 (s, 9H); 1.94-2.04 (m, 2H); 2.70 (t, 2H,
3J
HH=6.9Hz); 4.10 (t, 2H,
3J
HH=4.5Hz); 6.28 (d, 1H,
3J
HH=8.4Hz); 6.52 (d, 1H,
3J
HH=8.4Hz); 7.28-7.46 (m, 5h); 7.74 (s, 1H, NH). ultimate analysis, C
21H
23ClN
2O
3: calculated value (%) C:65.20; H:5.99; N:7.24. measured value (%) C:64.96; H:6.02; 7.37.
Embodiment 2:
Present embodiment explanation compound N '-tertiary butyl-N-5-chlorobenzene and dihydropyrane-6-formyl hydrazine (Compound I I, R
1The synthesizing=tertiary butyl)
1.1g (5mmol) 5-chlorobenzene and dihydropyrane-6-formic acid (III) is dissolved in the sulfur oxychloride of 1mL, temperature rising reflux 1h, decompression steams excessive sulfur oxychloride, resistates is dissolved in the 5mL methylene dichloride, with this solution down in the ice bath cooling, be added drop-wise to and be mixed with 1.25g (10mmol) tertiary butyl hydrazonium salt hydrochlorate, 0.70g (25mmol) sodium hydroxide, in the mixture of 15mL methylene dichloride and 5mL water, drip and finish room temperature reaction 6h again, add the 50mL ethyl acetate, tell organic layer, organic layer is water, saturated brine washing successively, anhydrous sodium sulfate drying.After filtering precipitation, the gained solid through cold ether wash white solid 1.1g.Yield: 78.6%.mp:117-120 ℃.
1H NMR δ: 1.18 (s, 9H); 2.01-2.09 (m, 2H); 2.81 (t, 2H, J=6.6Hz); 4.17 (t, 2H, J=5.1Hz); 6.79 (d, 1H, J=8.1Hz); 7.40 (d, 1H, J=8.1Hz). ultimate analysis, C
14H
19ClN
2O
2: calculated value (%) C:59.47; H:6.77. measured value (%) C:59.22; H:6.70.
Embodiment 3:
Synthesizing of present embodiment explanation compound 5-chlorobenzene and dihydropyrane-6-formic acid (compound III)
164g (1.0mol) the 2-tertiary butyl-4-methylphenol (a) is dissolved in 200mL toluene, the sodium hydroxide solution and 32.2g (0.01mol) tetra-n-butyl ammonium bromide that add 150g concentration 32%, the ice bath cooling drips 42g (1.20mol) 3-bromo-1-propine down, finishes, temperature control reacts 4h down at 35-40 ℃ again, after the reaction mixture cooling, add the dilution of 1000mL ethyl acetate, tell organic layer, organic layer is water, saturated brine washing successively, anhydrous sodium sulfate drying.After filtering precipitation, get the yellow oil 2-tertiary butyl-4-methyl isophthalic acid-(third-2-alkynyloxy group) benzene (b) 196.4g.Yield: 97.2%.
1H NMR δ: 1.31 (s, 9H); 2.21 (s, 3H); 2.39 (t, 1H, J=2.4Hz); 4.62 (d, 2H, J=2.4Hz); 6.78 (d, 1H, J=8.1Hz); 6.89-7.02 (m, 2H).
202g (1.0mol) the 2-tertiary butyl-4-methyl isophthalic acid-(third-2-alkynyloxy group) benzene (b) is dissolved in 150mL N, the N-Diethyl Aniline, temperature rising reflux 5h, be cooled to room temperature, add the dilution of 500mL ethyl acetate, tell organic layer, organic layer is used dilute hydrochloric acid (2M), water, saturated brine washing, anhydrous sodium sulfate drying successively.After filtering precipitation, the cut 173.5g of 98-100 ℃/85Pa is collected in the residuum underpressure distillation, promptly gets the 8-tertiary butyl-6-methyl-2H-chromene (c).Yield: 85.9%.
1H NMR δ: 1.28 (s, 9H); 2.18 (s, 3H); 4.61-4.63 (m, 2H); 5.72-5.77 (m, 1H); 6.31-6.36 (m, 1H); 6.61-6.86 (m, 2H). ultimate analysis, C
14H
18O: calculated value (%) C:83.12; H:8.97. measured value (%): C:82.96; H:8.79.
140g (0.69mol) the 8-tertiary butyl-6-methyl-2H-chromene (c) is dissolved in the 500mL methyl alcohol, the palladium carbon (moisture 60%) that adds 12.0g10%, logical hydrogen 5h under the stirring at room, decompress filter, after filtrate decompression concentrates, the cut 126g of 92-95 ℃/100Pa is collected in the residuum underpressure distillation, promptly gets the 8-tertiary butyl-6-methyl-chroman (d).Yield: 89.5%.
1H NMR δ: 1.28 (s, 9H); 1.85-1.93 (m, 2H); 2.16 (s, 3H); 2.69 (t, 2H, J=6.0Hz); 4.07 (t, 2H, J=5.1Hz); 6.65 (s, 1H); 6.81 (s, 1H). ultimate analysis, C
14H
20O: calculated value (%) C:82.30; H:9.87. measured value (%): C:82.19; H:9.78.
126g (0.62mol) the 8-tertiary butyl-6-methyl-chroman (d) is dissolved in the 200mL methylene dichloride, temperature control 30-35 ℃ of methylene dichloride (200mL) solution that drips 89.2g (0.66mol) sulfuryl chloride down, drip and finish, continuation is reacted 3h down at 30-35 ℃, after the reaction mixture cooling, water, saturated brine washing successively, anhydrous sodium sulfate drying.After filtering precipitation, get the white solid 8-tertiary butyl-5-chlorine 6-methyl chroman (e) 115.3g, yield: 78.0%.mp:44-46 ℃.
1H NMR δ: 1.27 (s, 9H); 1.90-1.99 (m, 2H); 2.22 (s, 3H); 2.72 (t, 2H, J=6.9Hz); 4.04 (t, 2H, J=5.1Hz); 6.90 (s, 1H). ultimate analysis, C
14H
19ClO: calculated value (%) C:70.43; H:8.02. measured value (%): C:70.32; H:7.95.
19.2g (0.08mol) the 8-tertiary butyl-5-chlorine 6-methyl chroman (e) is dissolved in the 100mL Glacial acetic acid, under 15 ℃ of the temperature controls, drip the aqueous acetic acid (80mL HAc+40mL water) of 24g (0.24mo) chromium trioxide, drip complete temperature control 10-15 ℃ and continue reaction 3-4h down, reaction mixture is poured in the frozen water, with ethyl acetate extraction, organic layer is successively with sodium bicarbonate, water, saturated brine washing, anhydrous sodium sulfate drying.After filtering precipitation, residuum gets the clear crystal 8-tertiary butyl-5-chlorobenzene and dihydropyrane-6-formaldehyde (f) 3.66g through the decompression column chromatography for separation.Yield: 18.1%.mp:174-175 ℃.
1H NMR δ: 1.37 (s, 9H); 2.05-2.13 (m, 2H); 2.87 (t, 2H, J=6.9Hz); 4.28 (t, 2H, J=4.5Hz; 7.77 (s, 1H); 10.39 (s, 1H). ultimate analysis, C
14H
17ClO
2: calculated value (%) C:66.53; H:6.78. measured value (%): C:66.48; H:6.70.
7.6g (0.03mol) the 8-tertiary butyl-5-chlorobenzene and dihydropyrane-6-formaldehyde (f) are dissolved in the 60mL methylene dichloride, dropwise add in the 60mL dichloromethane solution of hanging floating 8.01g (0.06mol) aluminum chloride by the feet down in the ice bath cooling again, drip and finish room temperature reaction 2h again, reaction mixture is poured in the hydrochloric acid of 50mL (1M), tell organic layer, successively with sodium bicarbonate, water, saturated brine washing, anhydrous sodium sulfate drying.After filtering precipitation, residuum gets clear crystal 5-chlorobenzene and dihydropyrane-6-formaldehyde (g) 3.82g through the decompression column chromatography for separation.Yield: 65.0%.mp:63-65 ℃.
1H NMR δ: 2.04-2.12 (m, 2H); 2.84 (t, 2H, J=6.0Hz); 4.23 (t, 2H, J=5.4Hz); 6.82 (d, 1H, J=8.4Hz); 7.73 (d, 1H, J=8.4Hz); 10.37 (s, 1H). ultimate analysis, C
10H
9ClO
2: calculated value (%) C:61.08; H:4.61. measured value (%): C:60.96; H:4.45.
6.14g (0.036mol) Silver Nitrate is dissolved in the 30mL water, water (15mL) solution that adds 1.6g (0.04mol) sodium hydroxide, stir 5min, collect silver suboxide through centrifugation, distilled water wash 3 times of gained silver suboxide, transfer in the three-necked bottle, stir and add 70mL water and 3.3g (0.083mol) sodium hydroxide down, this mixture heating up is arrived 55-60 ℃, 7.10g (0.036mol) 5-chlorobenzene and dihydropyrane-6-formaldehyde (g) are joined in the said mixture, continue reaction 15min, filter, precipitation is with hot wash, and filtrate is stirred down and poured in 1: 1 the hydrochloric acid of 40mL, collect white precipitate after filtration, this precipitation gets white solid 5-chlorobenzene and dihydropyrane-6-formic acid (compound III) 6.96g through 70% ethyl alcohol recrystallization.Yield: 91.0%.mp:202-205 ℃.
1H NMR δ: 1.98-2.14 (m, 2H); 2.85 (t, 2H, J=6.3Hz); 4.20 (t, 2H, J=5.4Hz); 6.79 (d, 1H, J=8.4Hz); 7.85 (d, 1H, J=8.4Hz) ultimate analysis, C
10H
9ClO
3: calculated value (%) C:56.49; H:4.27. measured value (%): C:56.47; H:4.44.
Compound of the present invention has carried out the mensuration of insecticidal activity, and the mensuration program is as follows:
For the examination insect is southern mythimna separata [Mythimna (=Pseudaletia) separata (Walker), the normal population that indoor leaf of Semen Maydis is raised.Mythimna separata is adopted leaf dipping method, and sample is mixed with the solution of different concns with acetone, and dipping leaf of Semen Maydis in seedling stage is put into the 7cm culture dish after drying, insert 4 instar larvaes, repeats 2-4 time.Contrast acetone soln soaking maize leaf breeding grub.At any time add fresh maize leaf after 24 hours.24 hours, 48 hours, 72 hours, 96 hours viewing test results, normally casting off a skin until control larvae became for 5 ages.Dead fully with armyworm larvae, that promptly touches motionlessly is the death standard of larva.
The present invention goes back the part of compounds of listing among the free list 1-3 and illustrates, but does not limit the present invention.
Table 1: the materialization data of part of compounds
| Compound | ????R 1 | ??R 2 | Fusing point (℃) | Yield (%) |
| ????1 | ????C(CH 3) 3 | ??Ph | ??247-248 | ????76.2 |
| ????2 | ????C(CH 3) 3 | ??2-Me-Ph | ??256-257 | ????76.2 |
| ????3 | ????C(CH 3) 3 | ??3-Me-Ph | ??235-237 | ????80.9 |
| ????4 | ????C(CH 3) 3 | ??4-Me-Ph | ??252-253 | ????85.7 |
| ????5 | ????C(CH 3) 3 | ??2，4-di-Me-Ph | ??194-195 | ????77.3 |
| ????6 | ????C(CH 3) 3 | ??3，5-di-Me-Ph | ??259-261 | ????55.2 |
| ????7 | ????C(CH 3) 3 | ??2，4，6-tri-Me-Ph | ??272-273 | ????56.5 |
| ????8 | ????C(CH 3) 3 | ??2-MeO-Ph | ??201-202 | ????72.7 |
| ????9 | ????C(CH 3) 3 | ??3-MeO-Ph | ??201-202 | ????77.3 |
| ????10 | ????C(CH 3) 3 | ??4-MeO-Ph | ??243-245 | ????72.0 |
| ????11 | ????C(CH 3) 3 | ??3，4-di-MeO-Ph | ??221-223 | ????83.3 |
| ????12 | ????C(CH 3) 3 | ??3，4，5-tri-MeO-Ph | ??230-231 | ????84.0 |
| ????13 | ????C(CH 3) 3 | ??4-C 2H 5O-Ph | ??213-214 | ????78.3 |
| ????14 | ????C(CH 3) 3 | ??2-Cl-Ph | ??236-237 | ????81.8 |
| ????15 | ????C(CH 3) 3 | ??3-Cl-Ph | ??232-233 | ????68.2 |
| ????16 | ????C(CH 3) 3 | ??4-Cl-Ph | ??243-246 | ????80.5 |
| ????17 | ????C(CH 3) 3 | ??2，4-di-Cl-Ph | ??142-145 | ????75.0 |
| ????18 | ????C(CH 3) 3 | ??3，5-di-Cl-Ph | ??253-255 | ????70.8 |
| ????19 | ????C(CH 3) 3 | ??2，4，6-tri-Cl-Ph | ??245-247 | ????58.8 |
| ????20 | ????C(CH 3) 3 | ??2-NO 2-4-Cl-Ph | ??215-216 | ????48.0 |
| ????21 | ????C(CH 3) 3 | ??2-Cl-4-NO 2-Ph | ??182-185 | ????60.0 |
| ????22 | ????C(CH 3) 3 | ??2，6-di-Cl-4-CF 3-Ph | ??233-234 | ????64.3 |
| ????23 | ????C(CH 3) 3 | ??2-F-Ph | ??228-230 | ????66.7 |
| ????24 | ????C(CH 3) 3 | ??2，4-di-F-Ph | ??165-166 | ????68.2 |
| ????25 | ????C(CH 3) 3 | ??3-I-Ph | ??249-251 | ????74.1 |
| ????26 | ????C(CH 3) 3 | ??4-I-Ph | ??247-249 | ????77.8 |
| ????27 | ????C(CH 3) 3 | ??2-NO 2-Ph | ??261-264 | ????85.0 |
Table 2: part of compounds
1The HNMR data
| Compound | 1HNMR |
| 1 | 1.60(s，9H)；1.94-2.04(m，2H)；2.70(t，2H， 3J HH＝6.9Hz)；4.10(t，2H， 3J HH＝4.5Hz)；6.28(d，1H， 3J HH＝8.4Hz)；6.52(d，1H， 3J HH＝8.4Hz)；7.28-7.46(m，5H)；7.74(s，1H，NH) |
| 2 | 1.60(s，9H)；1.93-2.01(m，2H)；2.35(s，3H)；2.69(t，2H， 3J HH＝6.6Hz)；4.09(t，2H， 3J HH＝5.1Hz)； 6.03(d，1H， 3J HH＝8.1Hz)；6.48(d，1H， 3J HH＝8.1Hz)；7.08-7.27(m，4H)；7.67(s，1H，NH) |
| 3 | 1.58(s，9H)；1.94-2.04(m，2H)；2.31(s，3H)；2.70(t，2H， 3J HH＝6.0Hz)；4.10(t，2H， 3J HH＝5.1Hz)； 6.27(d，1H， 3J HH＝8.1Hz)；6.52(d，1H， 3J HH＝8.1Hz)；7.16-7.26(m，4H)；7.84(s，1H，NH) |
| 4 | 1.58(s，9H)；1.95-2.04(m，2H)；2.34(s，3H)；2.71(t，2H， 3J HH＝6.0Hz)；4.11(t，2H， 3J HH＝5.1Hz)； 6.34(d，1H， 3J HH＝8.4Hz)；6.54(d，1H， 3J HH＝8.4Hz)；7.23(dd，4H， 3J HH＝7.5Hz)；7.77(s，1H， NH) |
| 5 | 1.61(s，9H)；1.90-2.05(m，2H)；2.22-2.40(m，6H)；2.64-2.76(m，2H)；4.04-4.17(m，2H)；6.05-6.15 (m，1H)；6.46-6.56(m，1H)；6.88-7.16(m，3H)；7.49(s，1H，NH) |
| 6 | 1.60(s，9H)；1.95-2.04(m，2H)；2.27(s，6H)；2.72(t，2H， 3J HH＝6.0Hz)；4.11(t，2H， 3J HH＝5.4Hz)； 6.34(d，1H， 3J HH＝9.3Hz)；6.56(d，1H， 3J HH＝9.3Hz)；6.99(s，1H)；7.06(s，2H)；7.56(s，1H，NH) |
| 7 | 1.64(s，9H)；1.94-2.02(m，2H)；2.21(s，3H)；2.26(s，3H)；2.35(s，3H)；2.70(t，2H， 3J HH＝6.0Hz)； 4.11(t，2H， 3J HH＝4.5Hz)；5.95(d，1H， 3J HH＝8.4Hz)；6.49(d，1H， 3J HH＝8.4Hz)；6.9-6.88(m， 2H)；7.70(s，1H，NH) |
| 8 | 1.62(s，9H)；1.95-2.05(m，2H)；2.71(t，2H， 3J HH＝6.6Hz)；3.82(s，3H)；4.11(t，2H， 3J HH＝5.1Hz)； 6.14(d，1H， 3J HH＝6.0Hz)；6.52(d，1H， 3J HH＝6.0Hz)；6.84-7.45(m，4H)；8.01(s，1H，NH) |
| 9 | 1.58(s，9)；1.94-2.02(m，2H)；2.70(t，2H， 3J HH＝6.9Hz)；3.77(s，3H)；4.11(t，2H， 3J HH＝5.4Hz)； 6.36(d，1H， 3J HH＝8.1Hz)；6.54(d，1H， 3J HH＝8.1Hz)；6.88-7.23(m，4H)；7.75(s，1H，NH) |
| 10 | 1.58(s，9H)；1.95-2.05(m，2H)；2.71(t，2H， 3J HH＝6.9Hz)；3.79(s，3H)；4.11(t，2H， 3J HH＝5.4Hz)； 6.50(d，1H， 3J HH＝8.4Hz)；6.58(d，1H， 3J HH＝8.4Hz)；7.13(dd，4H， 3J HH＝9.0Hz)；7.83(s，1H， NH) |
| 11 | 1.60(s，9H)；1.96-2.04(m，2H)；2.72(t，2H， 3J HH＝6.0Hz)；3.86(s，3H)；3.87(s，3H)；4.12(t，2H， 3J HH＝5.1Hz)；6.60-7.13(m，5H)；7.73(s，1H，NH) |
| 12 | 1.60(s，9H)；1.96-2.03(m，2H)；2.71(t，2H， 3J HH＝6.9Hz)；3.82(s，6H)；3.84(s，3H)；4.13(t，2H， 3J HH＝5.4Hz)；6.60-6.76(m，4H)；7.67(s，1H，NH) |
| 13 | 1.40(t，3h， 3J HH＝6.9Hz)；1.58(s，9H)；1.95-2.04(m，2H)；2.72(t，2H， 3J HH＝6.9Hz)；4.02(q，2H， 3J HH＝6.9Hz)；4.11(t，2H， 3J HH＝5.4Hz)；6.50(d，1H， 3J HH＝9.3Hz)；6.58(d，1H， 3J HH＝9.3Hz)；7.12 (dd，4H， 3J HH＝9.0Hz)；7.79(s，1H，NH) |
| 14 | 1.62(s，9H)；1.95-2.03(m，2H)；2.70(t，2H， 3J HH＝6.9Hz)；4.11(t，2H， 3J HH＝5.4Hz)；6.30(d，1H， 3J HH＝8.4Hz)；6.55(d，1H， 3J HH＝8.4Hz)；7.28-7.46(m，4H)；7.81(s，1H，NH) |
| 15 | 1.58(s，9H)；1.95-2.04(m，2H)；2.71(t，2H， 3J HH＝6.9Hz)；4.12(t，2H， 3J HH＝4.5Hz)；6.52-6.61 (m，2H)；7.21-7.43(m，4H)；7.86(s，1H，NH) |
| 16 | 1.59(s，9H)；1.96-2.05(m，2H)；2.72(t，2H， 3J HH＝6.6Hz)；4.13(t，2H， 3J HH＝5.4Hz)；6.57-6.64 |
| (m，2H)；7.36(dd，4H， 3J HH＝8.4Hz)；7.74(s，1H，NH) | |
| 17 | 1.61(s，9H)；1.97-2.04(m，2H)；2.72(t，2H， 3J HH＝6.6Hz)；4.13(t，2H， 3J HH＝5.1Hz)；6.59-6.66 (m，2H)；7.26-7.45(m，3H)；7.91(s，1H，NH) |
| 18 | 1.59(s，9H)；1.97-2.05(m，2H)；2.73(t，2H， 3J HH＝6.9Hz)；4.14(t，2H， 3J HH＝5.4Hz)；6.67(d，1H， 3J HH＝9.0Hz)；6.81(d，1H， 3J HH＝9.0Hz)；7.33-7.36(m，3H)；7.78(s，1H，NH) |
| 19 | 1.63(s，9H)；1.97-2.05(m，2H)；2.73(t，2H， 3J HH＝6.6Hz)；4.14(t，2H， 3J HH＝5.4Hz)；6.68(d，1H， 3J HH＝9.3Hz)；6.81(d，1H， 3J HH＝9.3Hz)；7.26-7.34(m，2H)；7.82(s，1H，NH) |
| 20 | 1.62(s，9H)；1.93-2.03(m，2H)；2.68(t，2H， 3J HH＝6.9Hz)；4.13(t，2H， 3J HH＝5.4Hz)；6.67(d，1H， 3J HH＝8.4Hz)；6.85(d，1H， 3J HH＝8.4Hz)；7.57-7.66(m，2H)；7.92(s，1H，NH)；8.07(s，1H) |
| 21 | 1.62(s，9H)；1.95-2.03(m，2H)；2.68(t，2H， 3J HH＝6.6Hz)；4.13(t，2H， 3J HH＝5.1Hz)；6.65(d，1H， 3J HH＝9.0Hz)；6.86(d，1H， 3J HH＝9.0Hz)；7.67-8.25(m，4H) |
| I22 | 1.65(s，9H)；1.96-2.04(m，2H)；2.70(t，2H， 3J HH＝6.6Hz)；4.13(t，2H， 3J HH＝5.4Hz)；6.64(d，1H， 3J HH＝8.1Hz)；6.75(d，1H， 3J HH＝8.1Hz)；7.51(s，1H)；7.58(s，1H)；7.80(s，1H，NH) |
| 23 | 1.59(s，9H)；1.96-2.04(m，2H)；2.72(t，2H， 3J HH＝6.6Hz)；4.12(t，2H， 3J HH＝5.1Hz)；6.56-6.63 (m，2H)；6.97-7.52(m，4H)；7.72(s，1H，NH) |
| 24 | 1.60(s，9H)；1.99-2.04(m，2H)；2.72(t，2H， 3J HH＝6.6Hz)；4.13(t，2H， 3J HH＝5.1Hz)；6.61-6.92(m， 4H)；7.53-7.61(m，1H)；8.01(s，1H，NH) |
| 25 | 1.58(s，9H)；1.96-2.04(m，2H)；2.72(t，2H， 3J HH＝6.6Hz)；4.13(t，2H， 3J HH＝5.1Hz)；6.56-6.64(m， 2H)；7.03-7.08(m，1H)；7.45(d，1H， 3J HH＝7.5Hz)；7.69(d，1H， 3J HH＝6.9Hz)；7.76(s，1H)7.78(s， 1H，NH) |
| 26 | 1.57(s，9H)；1.95-2.04(m，2H)；2.72(t，2H， 3J HH＝6.9Hz)；4.13(t，2H， 3J HH＝5.1Hz)；6.47(d，1H， 3J HH＝8.4Hz)；6.61(d，1H， 3J HH＝8.4Hz)；7.40(dd，4H， 3J HH＝8.4Hz)；7.95(s，1H，NH) |
| 27 | 1.64(s，9H)；1.93-2.01(m，2H)；2.65(t，2H， 3J HH＝6.0Hz)；4.10(t，2H， 3J HH＝5.4Hz)；6.58(s，2H)； 7.47-7.68(m，3H)；7.92(s，1H，NH)；8.09(d，1H， 3J HH＝8.4Hz) |
| 28 | 1.62(s，9H)；1.92-2.05(m，2H)；2.68(t，2H， 3J HH＝6.0Hz)；4.11(t，2H， 3J HH＝5.4Hz)；6.64(d，1H， 3J HH＝8.1Hz)；6.75(d，1H， 3J HH＝8.1Hz)；7.52(t，4H， 3J HH＝7.5Hz)；7.90-7.95(m，2H)； 8.17-8.28(m，2H) |
| 29 | 1.61(s，9H)；1.93-2.05(m，2H)；2.69(t，2H， 3J HH＝6.6Hz)；4.12(t，2H， 3J HH＝5.1Hz)；6.63(d，1H， 3J HH＝9.0Hz)；6.78(d，1H， 3J HH＝9.0Hz)；7.83(s，1H，NH)；7.91(dd，4H， 3J HH＝8.1Hz) |
| 30 | 1.72(s，9H)；1.86-1.99(m，2H)；2.51-2.63(m，2H)；4.02-4.10(m，2H)；6.25-7.70(m，5H)；8.49(s， 1H，NH) |
| 31 | 1.61(s，9H)；1.96-2.06(m，4H)；2.67-2.77(m，4H)；4.09-4.17(m，4H)；6.39(d，1H， 3J HH＝9.0Hz)； 6.57(d，1H， 3J HH＝9.0Hz)；6.72(d，1H， 3J HH＝9.0Hz)；7.21(d，1H， 3J HH＝9.0Hz)；7.82(s，1H， NH) |
Table 3: the biological activity test result of part of compounds:
| 456789 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 press down food callosity rice mite | ????100 ????- ????100 ????0 ????- ????- ????100 ????100 ????100 ????90 ????100 ????- ????- ????100 ????100 ????20 ????100 ????100 ????0 ????100 ????100 ????- ????- ????- ????40 ????- ????95 ????0 ????- ????- | ????100 ????100 ????100 ????- ????100 ????100 ????80 ????95 ????45 ????0 ????100 ????100 ????100 ????100 ????100 ????0 ????100 ????100 ????- ????100 ????100 ????70 ????70 ????100 ????10 ????80 ????0 ????0 ????100 ????- | ??95 ??90 ??100 ??- ??90 ??95 ??55 ??70 ??10 ??0 ??90 ??95 ??100 ??100 ??100 ??0 ??100 ??90 ??- ??100 ??100 ??45 ??10 ??- ??0 ??30 ??- ??- ??- ??- | ????82.5 ????70 ????100 ????0 ????60 ????20 ????10 ????10 ????0 ????0 ????50 ????75 ????90 ????95 ????95 ????0 ????100 ????60 ????0 ????90 ????75 ????10 ????0 ????75 ????0 ????10 ????0 ????0 ????0 ????100 |
Illustrate: not test of "-" expression in the table.
Press down the food hydrazine:
The rice mite:
Claims (10)
1, a kind of N-5-chlorobenzene and dihydropyrane-6-formyl radical-N ', N '-two replaces two hydrazide kind compounds, it is characterized in that it has structure shown in the following general formula (I):
Wherein, in the general formula (I), R
1Represent 1-6 carbon alkyl, 1-6 halocarbon substituted alkyl, 1-6 carbon alkoxyalkyl, 3-6 carbene base, 3-6 halo carbene base, 3-6 carbyne base, 3-7 carbocyclic ring alkyl or 3-6 carbon alkyl; R
2Represent phenyl, pyridyl, naphthyl, chroman, 2,3-dihydro-1,4-Ben Bing dioxazine, 4H-1,3-Ben Bing dioxazine, 2,3-dihydro-cumarone, cumarone, benzothiazole, 1,3-benzoxazole, 1,2-benzoisoxazole, benzoglyoxaline, each group is unsubstituted; Or replaced by one or more following radicals: halogen, 1-4 carbon alkyl, 1-4 carbon alkoxyl group, 1-4 halocarbon substituted alkyl, 1-4 halocarbon are for alkoxyl group, 1-4 carbon alkoxyalkyl, 1-4 carbon alkylthio, 1-4 carbon alkyl sulphinyl, 1-4 carbon alkyl sulphonyl, nitro, cyano group, hydroxyl, carboxyl, 1-4 carbon alkyl-carbonyl or 1-4 carbon alkoxy carbonyl.
2, replace two hydrazide kind compounds according to claim 1 described two, it is characterized in that,
R
1Represent 1-4 carbon alkyl; R
2Represent phenyl, pyridyl, naphthyl, chroman, 2,3-dihydro-1,4-Ben Bing dioxazine, 4H-1,3-Ben Bing dioxazine, 2,3-dihydro-cumarone, cumarone, benzothiazole, 1,3-benzoxazole, 1,2-benzoisoxazole, benzoglyoxaline, each group is unsubstituted; Or replaced by one or more following radicals: halogen, 1-4 carbon alkyl, 1-4 carbon alkoxyl group, 1-4 halocarbon substituted alkyl, 1-4 halocarbon are for alkoxyl group, 1-4 carbon alkoxyalkyl, 1-4 carbon alkylthio, 1-4 carbon alkyl sulphinyl, 1-4 carbon alkyl sulphonyl, nitro, cyano group, hydroxyl, carboxyl, 1-4 carbon alkyl-carbonyl or 1-4 carbon alkoxy carbonyl.
3, replace two hydrazide kind compounds according to claim 1 described two, it is characterized in that: R
1Represent 1-4 carbon alkyl, R
2Represent phenyl, pyridyl, chroman, or each group is replaced by one or more following radicals: halogen, 1-4 carbon alkyl, 1-4 carbon alkoxyl group, 1-4 halocarbon substituted alkyl or nitro.
4, the synthetic intermediate of described two replacement two hydrazide kind compounds (I) of claim 1 has structure shown in the following general formula (II):
In the general formula (II), R
1Have and give definition in the claim 1.
5, the synthetic intermediate of the described compound of claim 4 (II) has structure shown in following (III):
6, claim 1 described two replaces the preparation method of two hydrazide kind compounds, it is characterized in that described general formula (I) prepares by following synthetic route:
Compound 5-chlorobenzene and dihydropyrane-6-formic acid III and excessive oxalyl chloride room temperature reaction in methylene dichloride, or reflux with excessive thionyl chloride, excessive oxalyl chloride is sloughed in decompression or thionyl chloride makes 5-chlorobenzene and dihydropyrane-6-formyl chloride IV, need not to be further purified, with compound V under the alkali lye effect, reaction obtains II, and Compound I I makes N-5-chlorobenzene and dihydropyrane-6-formyl radical-N ' with the compound VI reaction in the presence of acid binding agent, and N '-two replaces two hydrazides class chemical combination I; R in the formula
1, R
2Have and give definition in the claim 1.
7; the preparation method who replaces two hydrazide kind compounds according to claim 6 described two; it is characterized in that: oxalyl chloride that described compound 5-chlorobenzene and dihydropyrane-6-carboxylic acid III and 1.5-3.5 mole are doubly measured or thionyl chloride reaction make 5-chlorobenzene and dihydropyrane-6-formyl chloride IV; the hydrochloride reaction of the compound V that compound IV is doubly measured with the 1.5-2.5 mole in the presence of the sodium hydroxide that the 3-6 mole is doubly measured obtains Compound I I; the compound VI reaction that Compound I I doubly measures with the 1-1.2 mole in the presence of the acid binding agent triethylamine that the 1.2-1.5 mole is doubly measured makes N-5-chlorobenzene and dihydropyrane 6-formyl radical-N ', and N '-two replaces two hydrazide kind compound I.
8, the preparation method of the described compound of claim 5 (III) is characterized in that by following synthetic route preparation:
Compound a and propargyl bromide react in toluene under sodium hydroxide solution and the effect of phase-transfer catalyst tetra-n-butyl ammonium bromide and make compound b, compound b is in N, the heating cyclization obtains compound c in the N-Diethyl Aniline, compound c gets compound d through palladium carbon catalytic hydrogenation, compound d gets Verbindung through the sulfuryl chloride chlorination, Verbindung aqueous acetic acid oxidation through chromic oxide in acetic acid gets compound f, compound f is in methylene dichloride, take off the tertiary butyl through aluminum chloride and get compound g, compound g gets compound III through the silver suboxide oxidation.
9, preparation method according to the described compound of claim 8 (III), it is characterized in that: the 1-propargyl bromide that described compound a and 1.2-1.5 mole are doubly measured aqueous sodium hydroxide solution that the 1.2-1.5 mole is doubly measured and 0.01 mole doubly under the tetra-n-butyl ammonium bromide effect of amount in toluene reaction make compound b, the N that compound b is doubly measured in the 1.2-1.5 mole, the heating cyclization obtains compound c in the N-Diethyl Aniline, compound c gets compound d through the palladium carbon catalytic hydrogenation of catalytic amount, the sulfuryl chloride chlorination that compound d is doubly measured through the 1.0-1.2 mole gets Verbindung, the aqueous acetic acid oxidation of the chromic oxide that Verbindung is doubly measured through the 3-3.5 mole in acetic acid gets compound f, compound f is in methylene dichloride, the aluminum chloride of doubly measuring through the 2-2.5 mole takes off the tertiary butyl and gets compound g, and the silver suboxide oxidation that compound g doubly measures through the 1-1.2 mole gets compound III.
10, claim 1 described two replaces two hydrazide kind compounds as insect growth regulator(IGR), control lepidopteran class, Coleoptera class, Heteroptera class, Diptera class, Orthoptera class and Homoptera class insect.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200510013135 CN1654464A (en) | 2005-01-25 | 2005-01-25 | N,N'-disubstituted dihydrazides compound and its preparing process and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200510013135 CN1654464A (en) | 2005-01-25 | 2005-01-25 | N,N'-disubstituted dihydrazides compound and its preparing process and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1654464A true CN1654464A (en) | 2005-08-17 |
Family
ID=34894201
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200510013135 Pending CN1654464A (en) | 2005-01-25 | 2005-01-25 | N,N'-disubstituted dihydrazides compound and its preparing process and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1654464A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110698394A (en) * | 2019-10-25 | 2020-01-17 | 浙江工业大学 | 2- (2-chloronicotinamido) ethyl benzoate derivative and preparation method and application thereof |
| CN113698283A (en) * | 2021-09-15 | 2021-11-26 | 浙江泰莱医药科技有限公司 | Preparation method of salvia miltiorrhiza neoketone |
-
2005
- 2005-01-25 CN CN 200510013135 patent/CN1654464A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110698394A (en) * | 2019-10-25 | 2020-01-17 | 浙江工业大学 | 2- (2-chloronicotinamido) ethyl benzoate derivative and preparation method and application thereof |
| CN113698283A (en) * | 2021-09-15 | 2021-11-26 | 浙江泰莱医药科技有限公司 | Preparation method of salvia miltiorrhiza neoketone |
| CN113698283B (en) * | 2021-09-15 | 2024-01-05 | 浙江泰莱医药科技有限公司 | Preparation method of tanshinone |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Dillard et al. | Synthesis and antiinflammatory activity of some 2, 2-dimethyl-1, 2-dihydroquinolines | |
| NO178300B (en) | Therapeutic amides | |
| CN100488963C (en) | New thiobizole formanide derivative and its synthesis process and bioactivity | |
| KR20090130887A (en) | Amide derivative and pesticide containing such compound | |
| US4927824A (en) | Fungicidal trisubstituted 1,3,5-triazine-2,4,6-triones | |
| AU2020424232A1 (en) | 2-(1,2,4-triazolyl)benzoyl arylamine active compound for inhibiting wheat take-all pathogen | |
| JP2751309B2 (en) | Pyrazoles and insecticides, miticides, fungicides containing them as an active ingredient | |
| US4091018A (en) | Novel 1,2,3,4-tetrahydro-4-oxo-(-oxy-)-1-naphthylamines and method of preparation thereof | |
| CN1654464A (en) | N,N'-disubstituted dihydrazides compound and its preparing process and application thereof | |
| US4141984A (en) | N-(1,3,4-thiadiazol-2-yl)benzamides | |
| Yan et al. | Functional characterization of a binding protein for Type-II sex pheromones in the tea geometrid moth Ectropis obliqua Prout | |
| US4148625A (en) | Tetrahydroisophthalimide compounds | |
| KR20070106990A (en) | Anthelmintic imidazol-thiazole derivates | |
| SK54197A3 (en) | Benzisoxazole derivatives, preparation method thereof, pesticidal compositions containing them and their use for the control of pests | |
| CN103087022B (en) | Oxalyl-substituted-3-aryltetronate compounds, and preparations and applications thereof | |
| US5034410A (en) | Anthelmintically active benzenepropanamide derivatives | |
| CA1181403A (en) | 1-phenoxy(phenylthio)-4-arylalkynyloxy-benzene derivatives endowed with a juvenil hormonic and an acaricide activity | |
| Mandaf et al. | Microwave-induced synthesis and anti-nemic activity of 4-amino-3-mercapto-5-pyridin-2-yl-4H-1, 2, 4-triazole Schiff bases | |
| US4666935A (en) | Substituted maleimides and their use as fungicides for plant-pathogenic fungi | |
| JPH11302233A (en) | Fluorine-containing aniline compound | |
| JPH06340643A (en) | Oxazole or thiazole derivative, its production and herbicide | |
| US4271166A (en) | N-(1,3,4-Thiadiazol-2-yl)benzamides | |
| Cossey et al. | 174. Some anti-microbial compounds in the heterocyclic series. Part IV. Non-photosensitizing basic ethers in the benzothiazole series | |
| US4537888A (en) | Substituted benzoxazine derivatives and fungicidal use | |
| JP2020011914A (en) | Condensed heterocyclic compound having 1,4-benzo dioxane ring or salt thereof, and anti-juvenile hormone agent composed of the compound |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |