CN102276553A - 2-((1,3,4- thiadiazolyl)aminomethyl) phenol compound with bactericidal activity - Google Patents
2-((1,3,4- thiadiazolyl)aminomethyl) phenol compound with bactericidal activity Download PDFInfo
- Publication number
- CN102276553A CN102276553A CN201110170049A CN201110170049A CN102276553A CN 102276553 A CN102276553 A CN 102276553A CN 201110170049 A CN201110170049 A CN 201110170049A CN 201110170049 A CN201110170049 A CN 201110170049A CN 102276553 A CN102276553 A CN 102276553A
- Authority
- CN
- China
- Prior art keywords
- methyl
- amino
- thiadiazolyl group
- phenol
- phenyl
- 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.)
- Granted
Links
- XJNLYDUUNKUGNI-UHFFFAOYSA-N CCCc1nnc(NCc(cccc2)c2O)[s]1 Chemical compound CCCc1nnc(NCc(cccc2)c2O)[s]1 XJNLYDUUNKUGNI-UHFFFAOYSA-N 0.000 description 1
- XCNPCGFAPVJPOU-UHFFFAOYSA-N COc(cc1)ccc1-c1nnc(NCc2ccccc2O)[s]1 Chemical compound COc(cc1)ccc1-c1nnc(NCc2ccccc2O)[s]1 XCNPCGFAPVJPOU-UHFFFAOYSA-N 0.000 description 1
- 0 C[C@](C(C)=NNC)(*1=CCC**=C1)SC(N)=C Chemical compound C[C@](C(C)=NNC)(*1=CCC**=C1)SC(N)=C 0.000 description 1
- RCSSIJHCSQZVKH-UHFFFAOYSA-N Cc1cccc(CNc2nnc(-c3ccccc3)[s]2)c1O Chemical compound Cc1cccc(CNc2nnc(-c3ccccc3)[s]2)c1O RCSSIJHCSQZVKH-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Nitrogen- Or Sulfur-Containing Heterocyclic Ring Compounds With Rings Of Six Or More Members (AREA)
Abstract
The invention belongs to the technical field of pesticide, and specifically relates to a 2-((1,3,4-thiadiazolyl)aminomethyl) phenol compound with bactericidal activity. A structural formula of the compound is shown as a formula (I), wherein a phenyl ring in the formula contains a substituent R1, and a thiadiazole ring contains a substituent R2. If the substituent R1 represents -H, the R2 represents -CH3 or -CH2CH3 or n-Pr or i-Pr or -C6H5 or o-CH3OC6H4 or m-CH3C6H4 or p-CH3OC6H4 or p-ClC6H4; if the substituent R1 represents -CH3, the R2 represents -CH3 or -CH2CH3 or n-Pr or i-Pr or C6H4 or p-ClC6H4 or p-CH3OC6H4. The compound of the present invention can be applied to control of crop disease and fungus damage; besides, raw materials are easily available, and a synthesis is simple.
Description
Technical field
The invention belongs to technical field of pesticide, be specifically related to a kind of 2-((1,3, the 4-thiadiazolyl group) aminomethyl) oxybenzene compound with fungicidal activity.
Background technology
Amino methyl phenol or substituted-amino methylphenol are the very important organic compound of a class, have wide biological activity, are subjected to extensive concern always.Has the activity of short saluresis and diuresis as these compounds, well hypertension and anti-inflammatory activity; Translocator mGATl-mGAT4 to the murine γ-An Jidingsuan has good inhibition activity; Some amino methyl phenol that contains carborane radical shows high anti-cancer activity and low toxicity to the CT26 cancer cells, can be used as potential boron neutron capture therapy agent (BNCT); 4-quinolylamine (4-aminoquinoline) the compounds GSK369796 that contains amino methyl phenylol structural unit has good anti-malarial activity.In addition, the double-core metal complexes that is formed by substituted-amino methylphenol and Ni (II) metal-salt can be used as the efficient functionalization model molecule of phosphohydrolase.
But, anti-inflammatory that we find to study at most in the document is the synthetic of amino methyl phenol or alkyl substituted-amino methylphenol compounds and they aspect medical and antitumour activity etc., and 2-((1,3,4-thiadiazolyl group) aminomethyl) the research report of phenol compound synthetic and the fungicidal activity aspect agricultural thereof is less.
Summary of the invention
The object of the present invention is to provide a kind of difference 2-with fungicidal activity ((1,3, the 4-thiadiazolyl group) aminomethyl) oxybenzene compound in the past.
2-of the present invention ((1,3, the 4-thiadiazolyl group) aminomethyl) oxybenzene compound, its structural formula is:
In the formula, substituent R is arranged on the phenyl ring
1, on the thiadiazoles ring substituent R is arranged
2
Work as substituent R
1Be-during H: R
2Be-CH
3Or-CH
2CH
3Or n-Pr or i-Pr or-C
6H
5Or o-CH
3OC
6H
4Or m-CH
3C
6H
4Or p-CH
3OC
6H
4Or p-C1C
6H
4
Work as substituent R
1Be-CH
3The time: R
2Be-CH
3Or-CH
2CH
3Or n-Pr or i-Pr or C
6H
4Or p-C1C
6H
4Or p-CH
3OC
6H
4
2-((1 of the present invention, 3, the 4-thiadiazolyl group) oxybenzene compound aminomethyl) is preferably: 2-((5-methyl isophthalic acid, 3,4-thiadiazolyl group-2-amino) phenol methyl), 2-((5-ethyl-1,3,4-thiadiazolyl group-2-amino) methyl) phenol, 2-((5-n-propyl-1,3,4-thiadiazolyl group-2-amino) methyl) phenol, 2-((5-sec.-propyl-1,3,4-thiadiazolyl group-2-amino) phenol methyl), 2-((5-phenyl-1,3,4-thiadiazolyl group-2-amino) phenol methyl), 2-((5-(2-p-methoxy-phenyl)-1,3,4-thiadiazolyl group-2-amino) methyl) phenol, 2-((5-(3-aminomethyl phenyl)-1,3,4-thiadiazolyl group-2-amino) methyl) phenol, 2-((5-(4-p-methoxy-phenyl)-1,3,4-thiadiazolyl group-2-amino) phenol methyl), 2-((5-(4-chloro-phenyl-)-1,3,4-thiadiazolyl group-2-amino) phenol methyl), 2-((5-methyl isophthalic acid, 3,4-thiadiazolyl group-2-amino) methyl)-6-methylphenol, 2-((5-ethyl-1,3,4-thiadiazolyl group-2-amino) methyl)-the 6-methylphenol, 2-((5-n-propyl-1,3,4-thiadiazolyl group-2-amino) methyl)-and the 6-methylphenol, 2-((5-sec.-propyl-1,3,4-thiadiazolyl group-2-amino) methyl)-the 6-methylphenol, 2-((5-phenyl-1,3,4-thiadiazolyl group-2-amino) methyl)-6-methylphenol, 2-((5-(4-chloro-phenyl-)-1,3,4-thiadiazolyl group-2-amino) methyl)-the 6-methylphenol, 2-((5-(4-p-methoxy-phenyl)-1,3,4-thiadiazolyl group-2-amino) methyl)-the 6-methylphenol;
Its structural formula is respectively:
2-((5-methyl isophthalic acid, 3,4-thiadiazolyl group-2-amino) methyl) phenol:
2-((5-ethyl-1,3,4-thiadiazolyl group-2-amino) methyl) phenol:
2-((5-n-propyl-1,3,4-thiadiazolyl group-2-amino) methyl) phenol:
2-((5-sec.-propyl-1,3,4-thiadiazolyl group-2-amino) methyl) phenol:
2-((5-phenyl-1,3,4-thiadiazolyl group-2-amino) methyl) phenol:
2-((5-(2-p-methoxy-phenyl)-1,3,4-thiadiazolyl group-2-amino) methyl) phenol:
2-((5-(3-aminomethyl phenyl)-1,3,4-thiadiazolyl group-2-amino) methyl) phenol:
2-((5-(4-p-methoxy-phenyl)-1,3,4-thiadiazolyl group-2-amino) methyl) phenol:
2-((5-(4-chloro-phenyl-)-1,3,4-thiadiazolyl group-2-amino) methyl) phenol:
2-((5-methyl isophthalic acid, 3,4-thiadiazolyl group-2-amino) methyl)-6-methylphenol:
2-((5-ethyl-1,3,4-thiadiazolyl group-2-amino) methyl)-6-methylphenol:
2-((5-n-propyl-1,3,4-thiadiazolyl group-2-amino) methyl)-6-methylphenol:
2-((5-sec.-propyl-1,3,4-thiadiazolyl group-2-amino) methyl)-6-methylphenol:
2-((5-phenyl-1,3,4-thiadiazolyl group-2-amino) methyl)-6-methylphenol:
2-((5-(4-chloro-phenyl-)-1,3,4-thiadiazolyl group-2-amino) methyl)-6-methylphenol:
2-((5-(4-p-methoxy-phenyl)-1,3,4-thiadiazolyl group-2-amino) methyl)-6-methylphenol:
Compound of the present invention can be applicable to the germ evil control of farm crop, and raw material is easy to get, and is synthetic simple.
Embodiment
The fungicidal activity of 2-of the present invention ((1,3, the 4-thiadiazolyl group) aminomethyl) oxybenzene compound is described below in conjunction with specific examples.
With botrytis cinerea pers (Botrytis cinerea), fusarium graminearum (Gibberella zeae), Phytophthora capsici germ (phytophythora capsici) and tobacco brown spot pathogen (Alternaria alternata) are for supplying the examination material, adopt toxic medium therapy, in general sieve concentration is under the 25mg/L, to 2-((5-methyl isophthalic acid, 3,4-thiadiazolyl group-2-amino) phenol methyl), 2-((5-ethyl-1,3,4-thiadiazolyl group-2-amino) phenol methyl), 2-((5-n-propyl-1,3,4-thiadiazolyl group-2-amino) phenol methyl), 2-((5-sec.-propyl-1,3,4-thiadiazolyl group-2-amino) phenol methyl), 2-((5-phenyl-1,3,4-thiadiazolyl group-2-amino) phenol methyl), 2-((5-(2-p-methoxy-phenyl)-1,3,4-thiadiazolyl group-2-amino) methyl) phenol, 2-((5-(3-aminomethyl phenyl)-1,3,4-thiadiazolyl group-2-amino) methyl) phenol, 2-((5-(4-p-methoxy-phenyl)-1,3,4-thiadiazolyl group-2-amino) phenol methyl), 2-((5-(4-chloro-phenyl-)-1,3,4-thiadiazolyl group-2-amino) phenol methyl), 2-((5-methyl isophthalic acid, 3,4-thiadiazolyl group-2-amino) methyl)-6-methylphenol, 2-((5-ethyl-1,3,4-thiadiazolyl group-2-amino) methyl)-the 6-methylphenol, 2-((5-n-propyl-1,3,4-thiadiazolyl group-2-amino) methyl)-and the 6-methylphenol, 2-((5-sec.-propyl-1,3,4-thiadiazolyl group-2-amino) methyl)-the 6-methylphenol, 2-((5-phenyl-1,3,4-thiadiazolyl group-2-amino) methyl)-6-methylphenol, 2-((5-(4-chloro-phenyl-)-1,3,4-thiadiazolyl group-2-amino) methyl)-the 6-methylphenol, 2-((5-(4-p-methoxy-phenyl)-1,3,4-thiadiazolyl group-2-amino) methyl)-the 6-methylphenol carried out the fungicidal activity test.Fungicidal activity is represented with the inhibition percentage.Handle incidence and the mycelial growth situation of back routine observation record blade, plant,, calculate preventive effect and inhibiting rate according to disease index and hyphal diameter.Test result sees Table 1.
The fungicidal activity of table 1 compound
As known from Table 1,2-((1,3, the 4-thiadiazolyl group) phenol active best to brown spot pathogen aminomethyl), 2-((5-(3-aminomethyl phenyl)-1 wherein, 3,4-thiadiazolyl group-2-amino) phenol methyl), 2-((5-(4-p-methoxy-phenyl)-1,3,4-thiadiazolyl group-2-amino) methyl) phenol, 2-((5-(4-chloro-phenyl-)-1,3,4-thiadiazolyl group-2-amino) phenol methyl), 2-((5-ethyl-1,3,4-thiadiazolyl group-2-amino) methyl)-6-methylphenol and 2-((5-n-propyl-1,3,4-thiadiazolyl group-2-amino) methyl)-activity of 6-methylphenol is 70%-76%.Secondly, compound all has certain activity to phytophthora root rot bacterium and ash arrhizus bacteria, compound 2-((5-(4-p-methoxy-phenyl)-1 wherein, 3,4-thiadiazolyl group-2-amino) methyl) phenol and 2-((5-n-propyl-1,3,4-thiadiazolyl group-2-amino) methyl)-the 6-methylphenol is respectively 51% to the activity of phytophthora root rot bacterium, 50%, compound 2-((5-phenyl-1,3,4-thiadiazolyl group-2-amino) methyl) phenol, 2-((5-(4-p-methoxy-phenyl)-1,3,4-thiadiazolyl group-2-amino) methyl) phenol and 2-((5-(4-chloro-phenyl-)-1,3,4-thiadiazolyl group-2-amino) methyl) phenol is 46% to the activity of ash arrhizus bacteria.
For a better understanding of the present invention, now provide the example of preparation 2-((1,3, the 4-thiadiazolyl group) aminomethyl) oxybenzene compound, the present invention includes but be not limited thereto the preparation method.
Synthesizing of example 1:2-((5-methyl isophthalic acid, 3,4-thiadiazolyl group-2-amino) methyl) phenol.
With salicylic aldehyde (6.11g, 0.05mol) and 2-amino-5-methyl isophthalic acid, 3, (5.76g 0.05mol) is dissolved in the dehydrated alcohol 4-thiadiazoles.Feed nitrogen then, add tosic acid (10mol%), stir and the heating reflux reaction mixture stopped reaction behind the 5h (TLC detection).To react the products therefrom Schiff's base and be cooled to 0 ℃, in 30min, add NaBH in batches with ice-water-bath
4(2.15g 0.055mol), treats NaBH
4After adding, continue down to stir 30min so that react completely at 0 ℃.The decompression precipitation adds ethyl acetate (200mL) to residue and dilutes and carry out extracting and separating.With organic layer water successively (2 * 100mL), (2 * 100mL) washings and are used Na to saturated aqueous common salt
2SO
4Drying is filtered, the decompression precipitation.Thick product behind the precipitation is carried out recrystallization with ethyl acetate/petroleum ether, obtain white solid product, productive rate 70%, fusing point (mp): 199.2-199.9 ℃.
1H?NMR(CDCl
3，500MHz)δ：9.76(s，1H，OH)，7.92(t，J＝?5.5Hz，1H，NH)，7.09(d，J＝6.5Hz，1H)，7.08(t，J＝7.5Hz，1H)，6.83(d，J＝8.0Hz，1H)，6.76(t，J＝7.0Hz，1H)，4.36(d，J＝5.5Hz，2H，CH
2)，2.43(s，3H，CH
3)；?
13C?NMR(CDCl
3，125MHz)δ：168.76，155.18，152.92，128.86，128.14，124.62，118.76，115.27，43.18，15.19；IR(KBr)v：3449，3209，3076，3017，2917，1579，1456，1424，1270，1239，1205，752，687cm
-1。
Synthesizing of example 2:2-((5-ethyl-1,3,4-thiadiazolyl group-2-amino) methyl) phenol.
(6.11g, 0.05mol) with 2-amino-5-ethyl-1,3, (6.45g 0.05mol) is dissolved in the dehydrated alcohol 4-thiadiazoles with salicylic aldehyde.Feed nitrogen then, add tosic acid (10mol%), stir and the heating reflux reaction mixture stopped reaction behind the 5h (TLC detection).To react the products therefrom Schiff's base and be cooled to 0 ℃, in 30min, add NaBH in batches with ice-water-bath
4(2.15g 0.055mol), treats NaBH
4After adding, continue down to stir 30min so that react completely at 0 ℃.The decompression precipitation adds ethyl acetate (200mL) to residue and dilutes and carry out extracting and separating.With organic layer water successively (2 * 100mL), (2 * 100mL) washings and are used Na to saturated aqueous common salt
2SO
4Drying is filtered, the decompression precipitation.Thick product behind the precipitation is carried out recrystallization with ethyl acetate/petroleum ether, obtain white solid product, productive rate 58%, mp:179.5-180.8 ℃.
1H?NMR(CDCl
3，500MHz)δ：9.67(s，1H，OH)，7.95(t，J＝5.0Hz，1H，NH)，7.19(d，J＝8.0Hz，1H)，7.09(t，J＝8.0Hz，1H)，6.81(d，J＝8.0Hz，1H)，6.76(t，J＝7.5Hz，1H)，4.36(d，J＝5.5Hz，2H，CH
2)，2.80(q，J＝7.5Hz，2H，CH
2)，1.19(d，J＝80Hz，3H，CH
3)；
13C?NMR(CDCl
3，125MHz)δ：168.41，159.36，155.16，128.97，128.21，124.64，118.82，115.28，43.26，23.10，13.77；IR(KBr)v：3413，3199，3075，2984，2890，1605，1581，1457，1420，1365，1271，1233，1040，980，752，686cm
-1。
Synthesizing of example 3:2-((5-n-propyl-1,3,4-thiadiazolyl group-2-amino) methyl) phenol.
(6.11g, 0.05mol) with 2-amino-5-n-propyl-1,3, (7.15g 0.05mol) is dissolved in the dehydrated alcohol 4-thiadiazoles with salicylic aldehyde.Feed nitrogen then, add tosic acid (10mol%), stir and the heating reflux reaction mixture stopped reaction behind the 5h (TLC detection).To react the products therefrom Schiff's base and be cooled to 0 ℃, in 30min, add NaBH in batches with ice-water-bath
4(2.15g 0.055mol), treats NaBH
4After adding, continue down to stir 30min so that react completely at 0 ℃.The decompression precipitation adds ethyl acetate (200mL) to residue and dilutes and carry out extracting and separating.With organic layer water successively (2 * 100mL), (2 * 100mL) washings and are used Na to saturated aqueous common salt
2SO
4Drying is filtered, the decompression precipitation.Thick product behind the precipitation is carried out recrystallization with ethyl acetate/petroleum ether, obtain white solid product, productive rate 56%, mp:134.9-135.2 ℃.
1H?NMR(CDCl
3，500MHz)δ：9.72(s，1H，OH)，7.91(t，J＝5.0Hz，1H，NH)，7.20(d，J＝7.5Hz，1H)，7.09(t，J＝7.5Hz，1H)，6.82(d，J＝8.0Hz，1H)，6.76(t，J＝7.5Hz，1H)，4.37(d，J＝5.5Hz，2H，CH
2)，2.76(t，J＝7.5Hz，2H，CH
2)，1.62(m，2H，CH
2)，0.91(t，J＝7.5Hz，3H，CH
3)；
13C?NMR(CDCl
3，125MHz)δ：168.50，157.93，155.22，123.06，128.24，124.69，118.86，115.37，43.35，39.01，22.44，13.35；IR(KBr)v：3434，3108，3079，2958，1581，1454，1428，1259，1236，1176，1132，1101，1079，843，748，685cm
-1。
Synthesizing of example 4:2-((5-sec.-propyl-1,3,4-thiadiazolyl group-2-amino) methyl) phenol.
(6.11g, 0.05mol) with 2-amino-5-sec.-propyl-1,3, (7.15g 0.05mol) is dissolved in the dehydrated alcohol 4-thiadiazoles with salicylic aldehyde.Feed nitrogen then, add tosic acid (10mol%), stir and the heating reflux reaction mixture stopped reaction behind the 5h (TLC detection).To react the products therefrom Schiff's base and be cooled to 0 ℃, in 30min, add NaBH in batches with ice-water-bath
4(2.15g 0.055mol), treats NaBH
4After adding, continue down to stir 30min so that react completely at 0 ℃.The decompression precipitation adds ethyl acetate (200mL) to residue and dilutes and carry out extracting and separating.With organic layer water successively (2 * 100mL), (2 * 100mL) washings and are used Na to saturated aqueous common salt
2SO
4Drying is filtered, the decompression precipitation.Thick product behind the precipitation is carried out recrystallization with ethyl acetate/petroleum ether, obtain white solid product, productive rate 72%, mp:169.9-170.8 ℃.
1H?NMR(CDCl
3，500MHz)δ：10.54(s，1H，OH)，7.23～7.20(m，1H)，7.16-7.15(m，1H)，?7.00-6.98(m，1H)，6.85(t，J＝6.5Hz，1H)，4.51(d，J＝5.5Hz，2H，CH
2)，3.21(m，1H，CH)，1.33(d，J＝7.0Hz，6H，CH
3)；
13C?NMR(CDCl
3，125MHz)δ：169.41，166.74，156.00，130.75，129.85，124.58，120.04，118.71，45.84，30.99，22.78(2C)；IR(KBr)v：3430，3293，3112，2966，1576，1454，1428，1359，1259，1232，1090，841，749，689cm
-1。
Synthesizing of example 5:2-((5-phenyl-1,3,4-thiadiazolyl group-2-amino) methyl) phenol.
(6.11g, 0.05mol) with 2-amino-5-phenyl-1,3, (8.85g 0.05mol) is dissolved in the dehydrated alcohol 4-thiadiazoles with salicylic aldehyde.Feed nitrogen then, add tosic acid (10mol%), stir and the heating reflux reaction mixture stopped reaction behind the 5h (TLC detection).To react the products therefrom Schiff's base and be cooled to 0 ℃, in 30min, add NaBH in batches with ice-water-bath
4(2.15g 0.055mol), treats NaBH
4After adding, continue down to stir 30min so that react completely at 0 ℃.The decompression precipitation adds ethyl acetate (200mL) to residue and dilutes and carry out extracting and separating.With organic layer water successively (2 * 100mL), (2 * 100mL) washings and are used Na to saturated aqueous common salt
2SO
4Drying is filtered, the decompression precipitation.Thick product behind the precipitation is carried out recrystallization with ethyl acetate/petroleum ether, obtain white solid product, productive rate 73%, mp:209.7-210.4 ℃.
1H?NMR(DMSO-d6，500MHz)δ：9.75(s，1H，OH)，8.31(t，J＝5.5Hz，1H，NH)，7.74-7.76(m，2H)，7.42-7.48(m，3H)，7.25(d，J＝7.0Hz，1H)，7.11(t，J＝7.5Hz，1H)，6.78(t，J＝9Hz，1H)，6.84-6.86(m，1H)，4.69(d，J＝5.5Hz，2H，CH
2)；
13C?NMR(DMSO-d6，125MHz)δ：168.53，156.05，155.27，130.89，129.69，129.20(2C)，129.08，128.41，126.35(2C)，124.32，118.90，115.21，43.48；IR(KBr)v：3446，3320，3076，3032，2960，2841，1606，1576，1458，1470，1342，1252，1244，1173，1106，1030，836，802，766，750cm
-1。
Synthesizing of example 6:2-((5-(2-p-methoxy-phenyl)-1,3,4-thiadiazolyl group-2-amino) methyl) phenol.
(6.11g, 0.05mol) with 2-amino-5-o-methoxyphenyl-1,3, (10.36g 0.05mol) is dissolved in the dehydrated alcohol 4-thiadiazoles with salicylic aldehyde.Feed nitrogen then, add tosic acid (10mol%), stir and the heating reflux reaction mixture stopped reaction behind the 5h (TLC detection).To react the products therefrom Schiff's base and be cooled to 0 ℃, in 30min, add NaBH in batches with ice-water-bath
4(2.15g 0.055mol), treats NaBH
4After adding, continue down to stir 30min so that react completely at 0 ℃.The decompression precipitation adds ethyl acetate (200mL) to residue and dilutes and carry out extracting and separating.With organic layer water successively (2 * 100mL), (2 * 100mL) washings and are used Na to saturated aqueous common salt
2SO
4Drying is filtered, the decompression precipitation.Thick product behind the precipitation is carried out recrystallization with ethyl acetate/petroleum ether, obtain white solid product, productive rate 79%, mp:187.1-190.1 ℃.
1H?NMR(DMSO-d6，500MHz)δ：7.79～7.81(m，1H)，7.75(s，1H)，7.60(s，1H)，7.29-6.92(m，6H)，5.31(d，J＝5.5Hz，2H，CH
2)，3.82(s，3H，OCH
3)；
13C?NMR(DMSO-d6，125MHz)δ：168.49，156.16，155.26，138.48，130.82，130.29，129.08，128.99，128.36，126.77，123.50，122.97，118.88，115.26，43.51，20.84；IR(KBr)v：3383，3030，2921，2866，1600，1588，1455，1421，1354，1273，1239，1218，1099，987，795，762，691cm
-1。
Synthesizing of example 7:2-((5-(3-aminomethyl phenyl)-1,3,4-thiadiazolyl group-2-amino) methyl) phenol.
((9.55g 0.05mol) is dissolved in the dehydrated alcohol 4-thiadiazoles for 6.11g, aminomethyl phenyl-1,3 0.05mol) and between 2-amino-5-with salicylic aldehyde.Feed nitrogen then, add tosic acid (10mol%), stir and the heating reflux reaction mixture stopped reaction behind the 5h (TLC detection).To react the products therefrom Schiff's base and be cooled to 0 ℃, in 30min, add NaBH in batches with ice-water-bath
4(2.15g 0.055mol), treats NaBH
4After adding, continue down to stir 30min so that react completely at 0 ℃.The decompression precipitation adds ethyl acetate (200mL) to residue and dilutes and carry out extracting and separating.With organic layer water successively (2 * 100mL), (2 * 100mL) washings and are used Na to saturated aqueous common salt
2SO
4Drying is filtered, the decompression precipitation.Thick product behind the precipitation is carried out recrystallization with ethyl acetate/petroleum ether, obtain white solid product, productive rate 73%, mp:184.0-185.0 ℃.
1H?NMR(DMSO-d6，500MHz)δ：9.76(s，1H，OH)，8.31(t，?J＝5.5Hz，1H，NH)，7.56-7.54(m，2H)，7.35(t，J＝7.5Hz，1H)，7.26-7.24(m，2H)，7.11(t，J＝7.0Hz，1H)，6.86-6.84(m，1H)，6.78(t，J＝7.5Hz，1H)，4.60(d，J＝5.5Hz，2H，CH
2)，2.36(s，3H，CH
3)；
13CNMR(DMSO-d6，125MHz)δ：168.86，156.59，155.71，138.96，131.25，130.78，129.53，129.49，128.84，127.23，124.74，123.95，119.32，115.64，43.91，21.33；IR(KBr)v：3384，3030，2922，2866，1600，1538，1455，1354，1273，1239，1218，1099，987，795，760，691cm
-1。
Synthesizing of example 8:2-((5-(4-p-methoxy-phenyl)-1,3,4-thiadiazolyl group-2-amino) methyl) phenol.
(6.11g, 0.05mol) with 2-amino-5-p-methoxyphenyl-1,3, (10.36g 0.05mol) is dissolved in the dehydrated alcohol 4-thiadiazoles with salicylic aldehyde.Feed nitrogen then, add tosic acid (10mol%), stir and the heating reflux reaction mixture stopped reaction behind the 5h (TLC detection).To react the products therefrom Schiff's base and be cooled to 0 ℃, in 30min, add NaBH in batches with ice-water-bath
4(2.15g 0.055mol), treats NaBH
4After adding, continue down to stir 30min so that react completely at 0 ℃.The decompression precipitation adds ethyl acetate (200mL) to residue and dilutes and carry out extracting and separating.With organic layer water successively (2 * 100mL), (2 * 100mL) washings and are used Na to saturated aqueous common salt
2SO
4Drying is filtered, the decompression precipitation.Thick product behind the precipitation is carried out recrystallization with ethyl acetate/petroleum ether, obtain white solid product, productive rate 80%, mp:190.6-192.3 ℃.
1H?NMR(DMSO-d6，500MHz)δ：9.77(s，1H，OH)，8.22(t，J＝5.5Hz，1H)，7.67-7.69(m，1H)，7.24(d，J＝7.0Hz，1H)，7.11(t，J＝7.5Hz，1H)，7.01-7.03(m，2H)，6.83-6.85(m，1H)，6.78(t，J＝7.5Hz，1H)，4.45(d，J＝5.5Hz，2H，CH
2)，3.80(s，3H，OCH
3)；
13C?NMR(DMSO-d6，125MHz)δ：168.41，160.78，156.38，155.69，129.51，128.80，128.28(2C)，124.87，123.93，119.32，115.66，114.97(2C)，55.76，43.86；IR(KBr)v：3449，3323，3072，3035，2961，2839，1607，1578，1462，1474，1347，1254，1246，1175，1107，1033，837，802，767，750，609cm
-1。
Synthesizing of example 9:2-((5-(4-chloro-phenyl-)-1,3,4-thiadiazolyl group-2-amino) methyl) phenol.
(6.11g, 0.05mol) with 2-amino-5-rubigan-1,3, (10.55g 0.05mol) is dissolved in the dehydrated alcohol 4-thiadiazoles with salicylic aldehyde.Feed nitrogen then, add tosic acid (10mol%), stir and the heating reflux reaction mixture stopped reaction behind the 5h (TLC detection).To react the products therefrom Schiff's base and be cooled to 0 ℃, in 30min, add NaBH in batches with ice-water-bath
4(2.15g 0.055mol), treats NaBH
4After adding, continue down to stir 30min so that react completely at 0 ℃.The decompression precipitation adds ethyl acetate (200mL) to residue and dilutes and carry out extracting and separating.With organic layer water successively (2 * 100mL), (2 * 100mL) washings and are used Na to saturated aqueous common salt
2SO
4Drying is filtered, the decompression precipitation.Thick product behind the precipitation is carried out recrystallization with ethyl acetate/petroleum ether, obtain white solid product, productive rate 70%, mp:119.8-120.4 ℃.
1H?NMR(DMSO-d
6，500MHz)δ：9.75(s，1H，OH)，8.38(t，J＝5.5Hz，1H，NH)，7.78～7.76(m，2H)，7.54～7.52(m，2H)，7.24(d，J＝7.5Hz，1H)，7.11(t，J＝8.0Hz，1H)，6.85-6.83(m，1H)，6.78(t，J＝7.5Hz，1H)，4.47(d，J＝5.5Hz，2H，CH
2)；
13CNMR(DMSO-d
6，125MHz)δ：169.18，155.70，155.24，134.49，130.17，129.65(2C)，129.50，128.86，128.36(2C)，124.63，119.30，115.59，43.92；IR(KBr)v：3435，3256，2942，2923，1639，1571，1555，1418，1349，1210，1092，828，752，717cm
-1。
Synthesizing of example 10:2-((5-methyl isophthalic acid, 3,4-thiadiazolyl group-2-amino) methyl)-6-methylphenol.
With 6-methyl-2-hydroxy benzaldehyde (6.85g, 0.05mol) and 2-amino-5-methyl isophthalic acid, 3, (5.76g 0.05mol) is dissolved in the dehydrated alcohol 4-thiadiazoles.Feed nitrogen then, add tosic acid (10mol%), stir and the heating reflux reaction mixture stopped reaction behind the 5h (TLC detection).To react the products therefrom Schiff's base and be cooled to 0 ℃, in 30min, add NaBH in batches with ice-water-bath
4(2.15g 0.055mol), treats NaBH
4After adding, continue down to stir 30min so that react completely at 0 ℃.The decompression precipitation adds ethyl acetate (200mL) to residue and dilutes and carry out extracting and separating.With organic layer water successively (2 * 100mL), (2 * 100mL) washings and are used Na to saturated aqueous common salt
2SO
4Drying is filtered, the decompression precipitation.Thick product behind the precipitation is carried out recrystallization with ethyl acetate/petroleum ether, obtain white solid product, productive rate 68%, mp:173.6-174.5 ℃.
1H?NMR(CDCl
3，500MHz)δ：10.33(s，1H，OH)，7.10(d，J＝2.0Hz，1H)，7.01(d，J＝7.0Hz，1H)，6.78(t，J＝7.5Hz，1H)，5.80(s，1H，NH)，4.52(s，2H)，2.53(s，3H，CH
3)，2.28(s，3H，CH
3)。
13C?NMR(CDCl
3，125MHz)δ：169.75，154.96，154.09，130.96，128.58，127.82，124.45，119.75，45.29，16.67，15.80。IR(KBr)v：3435，3203，2002，2960，1595，1560，1523，1504，1341，1250，1199，1085，966，742cm
-1。
Synthesizing of example 11:2-((5-ethyl-1,3,4-thiadiazoles-2-amino) methyl)-6-methylphenol.
(6.85g, 0.05mol) with 2-amino-5-ethyl-1,3, (6.45g 0.05mol) is dissolved in the dehydrated alcohol 4-thiadiazoles with 6-methyl-2-hydroxy benzaldehyde.Feed nitrogen then, add tosic acid (10mol%), stir and the heating reflux reaction mixture stopped reaction behind the 5h (TLC detection).To react the products therefrom Schiff's base and be cooled to 0 ℃, in 30min, add NaBH in batches with ice-water-bath
4(2.15g 0.055mol), treats NaBH
4After adding, continue down to stir 30min so that react completely at 0 ℃.The decompression precipitation adds ethyl acetate (200mL) to residue and dilutes and carry out extracting and separating.With organic layer water successively (2 * 100mL), (2 * 100mL) washings and are used Na to saturated aqueous common salt
2SO
4Drying is filtered, the decompression precipitation.Thick product behind the precipitation is carried out recrystallization with ethyl acetate/petroleum ether, obtain white solid product, productive rate 63%, mp:175.7-177.5 ℃.
1H?NMR(CDCl
3，500MHz)δ：10.36(s，1H，OH)，7.10(d，J＝7.0Hz，1H)，7.00(d，J＝8.0Hz，1H)，6.78(t，J＝7.5Hz，1H)，5.74(s，1H，NH)，4.53(s，2H)，2.88(q，J＝2.5Hz，2H，CH
2)，2.28(s，3H)，1.31(t，J＝7.5Hz，3H，CH
3)。
13CNMR(CDCl
3，125MHz)δ：169.26，161.75，154.17，130.96，128.52，128.00，124.43，119.73，45.23，23.98，16.69，13.79。IR(KBr)v：3437，3221，3007，1595，1558，1520，1499，1341，1250，1136，1049，840，743cm
-1。
Synthesizing of example 12:2-((5-n-propyl-1,3,4-thiadiazoles-2-amino) methyl)-6-methylphenol.
(6.85g, 0.05mol) with 2-amino-5-n-propyl-1,3, (7.15g 0.05mol) is dissolved in the dehydrated alcohol 4-thiadiazoles with 6-methyl-2-hydroxy benzaldehyde.Feed nitrogen then, add tosic acid (10mol%), stir and the heating reflux reaction mixture stopped reaction behind the 5h (TLC detection).To react the products therefrom Schiff's base and be cooled to 0 ℃, in 30min, add NaBH in batches with ice-water-bath
4(2.15g 0.055mol), treats NaBH
4After adding, continue down to stir 30min so that react completely at 0 ℃.The decompression precipitation adds ethyl acetate (200mL) to residue and dilutes and carry out extracting and separating.With organic layer water successively (2 * 100mL), (2 * 100mL) washings and are used Na to saturated aqueous common salt
2SO
4Drying is filtered, the decompression precipitation.Thick product behind the precipitation is carried out recrystallization with ethyl acetate/petroleum ether, obtain white solid product, productive rate 66%, mp:148.7-150.3 ℃.
1H?NMR(CDCl
3，500MHz)δ：7.09(d，J＝7.5Hz，1H)，7.02(d，J＝7.5Hz，1H)，6.77(t，J＝7.5Hz，1H)，4.53(s，2H，CH
2)，2.83(t，J＝7.5Hz，2H)，2.28(s，3H，CH
3)，1.77～1.69(m，2H)，0.99(t，J＝10.5Hz，3H，CH
3)。
13C?NMR(DMSO-d
6，125MHz)δ：168.50，157.93，155.22，129.06，128.24，124.70，118.86，115.37，43.35，31.37，22.44，15.92，13.42。IR(KBr)v：3429，3203，2997，2962，1708，1596，1559，1518，1498，1340，1217，840，744cm
-1。
Synthesizing of example 13:2-((5-sec.-propyl-1,3,4-thiadiazoles-2-amino) methyl)-6-methylphenol.
(6.85g, 0.05mol) with 2-amino-5-sec.-propyl-1,3, (7.15g 0.05mol) is dissolved in the dehydrated alcohol 4-thiadiazoles with 6-methyl-2-hydroxy benzaldehyde.Feed nitrogen then, add tosic acid (10mol%), stir and the heating reflux reaction mixture stopped reaction behind the 5h (TLC detection).To react the products therefrom Schiff's base and be cooled to 0 ℃, in 30min, add NaBH in batches with ice-water-bath
4(2.15g 0.055mol), treats NaBH
4After adding, continue down to stir 30min so that react completely at 0 ℃.The decompression precipitation adds ethyl acetate (200mL) to residue and dilutes and carry out extracting and separating.With organic layer water successively (2 * 100mL), (2 * 100mL) washings and are used Na to saturated aqueous common salt
2SO
4Drying is filtered, the decompression precipitation.Thick product behind the precipitation is carried out recrystallization with ethyl acetate/petroleum ether, obtain white solid product, productive rate 65%, mp:163.3-163.8 ℃.
1H?NMR(CDCl
3，500MHz)δ：7.10(d，J＝7.5Hz，1H)，7.01(d，J＝7.0Hz，1H)，6.77(t，J＝9.0Hz，Hz，1H)，4.53(s，2H，CH
2)，3.23～3.18(m，1H，CH)，2.28(s，3H，CH
3)，1.45(d，J＝6.5Hz，6H)。
13C?NMR(DMSO-d
6，125MHz)δ：169.59，165.58，154.35，130.93，128.83，126.59，126.29，120.28，44.70，31.09，23.52(2C)，17.52。IR(KBr)v：3432，3210，3004，2963，1709，1595，1556，1521，1497，1346，1250，1133，1049，840，746cm
-1。
Synthesizing of example 14:2-((5-(4-chloro-phenyl-)-1,3,4-thiadiazolyl group-2-amino) methyl)-6-methylphenol.
(6.85g, 0.05mol) with 2-amino-5-rubigan-1,3, (10.55g 0.05mol) is dissolved in the dehydrated alcohol 4-thiadiazoles with 6-methyl-2-hydroxy benzaldehyde.Feed nitrogen then, add tosic acid (10mol%), stir and the heating reflux reaction mixture stopped reaction behind the 5h (TLC detection).To react the products therefrom Schiff's base and be cooled to 0 ℃, in 30min, add NaBH in batches with ice-water-bath
4(2.15g 0.055mol), treats NaBH
4After adding, continue down to stir 30min so that react completely at 0 ℃.The decompression precipitation adds ethyl acetate (200mL) to residue and dilutes and carry out extracting and separating.With organic layer water successively (2 * 100mL), (2 * 100mL) washings and are used Na to saturated aqueous common salt
2SO
4Drying is filtered, the decompression precipitation.Thick product behind the precipitation is carried out recrystallization with ethyl acetate/petroleum ether, obtain white solid product, productive rate 69%, mp:230.4-232.0 ℃.
1H?NMR(DMSO-d
6，500MHz)δ：7.76～7.74(m，2H)，7.52～7.50(m，2H)，7.01(d，J＝7.5Hz，1H)，6.71(t，J＝7.5Hz，1H)，4.47(s，2H，CH
2)，2.16(s，3H，CH
3)；
13CNMR(DMSO-d
6，125MHz)δ：170.02，156.06，154.20，135.30，131.05，130.55，130.28(2C)，129.04(2C)，128.41，126.33，125.99，120.43，44.94，17.60；IR(KBr)v：3434，3226，2988，2923，1714，1571，1555，1496，1349，1247，1092，1049，828，752，717cm
-1。
Claims (2)
1. 2-((1 with fungicidal activity, 3, the 4-thiadiazolyl group) aminomethyl) oxybenzene compound, its structural formula is:
In the formula, substituent R is arranged on the phenyl ring
1, on the thiadiazoles ring substituent R is arranged
2
Work as substituent R
1Be-during H: R
2Be-CH
3Or-CH
2CH
3Or n-Pr or i-Pr or-C
6H
5Or o-CH
3OC
6H
4Or m-CH
3C
6H
4Or p-CH
3OC
6H
4Or p-ClC
6H
4
Work as substituent R
1Be-CH
3The time: R
2Be-CH
3Or-CH
2CH
3Or n-Pr or i-Pr or C
6H
4Or p-ClC
6H
4Or p-CH
3OC
6H
4
2. the 2-((1 with fungicidal activity according to claim 1,3, the 4-thiadiazolyl group) oxybenzene compound aminomethyl), be preferably: 2-((5-methyl isophthalic acid, 3,4-thiadiazolyl group-2-amino) phenol methyl), 2-((5-ethyl-1,3,4-thiadiazolyl group-2-amino) phenol methyl), 2-((5-n-propyl-1,3,4-thiadiazolyl group-2-amino) methyl) phenol, 2-((5-sec.-propyl-1,3,4-thiadiazolyl group-2-amino) phenol methyl), 2-((5-phenyl-1,3,4-thiadiazolyl group-2-amino) phenol methyl), 2-((5-(2-p-methoxy-phenyl)-1,3,4-thiadiazolyl group-2-amino) methyl) phenol, 2-((5-(3-aminomethyl phenyl)-1,3,4-thiadiazolyl group-2-amino) methyl) phenol, 2-((5-(4-p-methoxy-phenyl)-1,3,4-thiadiazolyl group-2-amino) phenol methyl), 2-((5-(4-chloro-phenyl-)-1,3,4-thiadiazolyl group-2-amino) phenol methyl), 2-((5-methyl isophthalic acid, 3,4-thiadiazolyl group-2-amino) methyl)-6-methylphenol, 2-((5-ethyl-1,3,4-thiadiazolyl group-2-amino) methyl)-the 6-methylphenol, 2-((5-n-propyl-1,3,4-thiadiazolyl group-2-amino) methyl)-and the 6-methylphenol, 2-((5-sec.-propyl-1,3,4-thiadiazolyl group-2-amino) methyl)-the 6-methylphenol, 2-((5-phenyl-1,3,4-thiadiazolyl group-2-amino) methyl)-6-methylphenol, 2-((5-(4-chloro-phenyl-)-1,3,4-thiadiazolyl group-2-amino) methyl)-the 6-methylphenol, 2-((5-(4-p-methoxy-phenyl)-1,3,4-thiadiazolyl group-2-amino) methyl)-the 6-methylphenol;
Its structural formula is respectively:
2-((5-methyl isophthalic acid, 3,4-thiadiazolyl group-2-amino) methyl) phenol:
2-((5-ethyl-1,3,4-thiadiazolyl group-2-amino) methyl) phenol:
2-((5-n-propyl-1,3,4-thiadiazolyl group-2-amino) methyl) phenol:
2-((5-sec.-propyl-1,3,4-thiadiazolyl group-2-amino) methyl) phenol:
2-((5-phenyl-1,3,4-thiadiazolyl group-2-amino) methyl) phenol:
2-((5-(2-p-methoxy-phenyl)-1,3,4-thiadiazolyl group-2-amino) methyl) phenol:
2-((5-(3-aminomethyl phenyl)-1,3,4-thiadiazolyl group-2-amino) methyl) phenol:
2-((5-(4-p-methoxy-phenyl)-1,3,4-thiadiazolyl group-2-amino) methyl) phenol:
2-((5-(4-chloro-phenyl-)-1,3,4-thiadiazolyl group-2-amino) methyl) phenol:
2-((5-methyl isophthalic acid, 3,4-thiadiazolyl group-2-amino) methyl)-6-methylphenol:
2-((5-ethyl-1,3,4-thiadiazolyl group-2-amino) methyl)-6-methylphenol:
2-((5-n-propyl-1,3,4-thiadiazolyl group-2-amino) methyl)-6-methylphenol:
2-((5-sec.-propyl-1,3,4-thiadiazolyl group-2-amino) methyl)-6-methylphenol:
2-((5-phenyl-1,3,4-thiadiazolyl group-2-amino) methyl)-6-methylphenol:
2-((5-(4-chloro-phenyl-)-1,3,4-thiadiazolyl group-2-amino) methyl)-6-methylphenol:
2-((5-(4-p-methoxy-phenyl)-1,3,4-thiadiazolyl group-2-amino) methyl)-6-methylphenol:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110170049 CN102276553B (en) | 2011-06-23 | 2011-06-23 | 2-((1,3,4- thiadiazolyl)aminomethyl) phenol compound with bactericidal activity |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110170049 CN102276553B (en) | 2011-06-23 | 2011-06-23 | 2-((1,3,4- thiadiazolyl)aminomethyl) phenol compound with bactericidal activity |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102276553A true CN102276553A (en) | 2011-12-14 |
| CN102276553B CN102276553B (en) | 2013-04-10 |
Family
ID=45102341
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201110170049 Expired - Fee Related CN102276553B (en) | 2011-06-23 | 2011-06-23 | 2-((1,3,4- thiadiazolyl)aminomethyl) phenol compound with bactericidal activity |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102276553B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102757405A (en) * | 2012-07-25 | 2012-10-31 | 山东理工大学 | Vanilline derivative containing thiadiazole, preparation method and purpose thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1884269A (en) * | 2006-07-05 | 2006-12-27 | 浙江工业大学 | 2-[(2-methyl-4-hydroxy benzyl)azo]-1,3,4-thiadiazole and its preparation and use |
-
2011
- 2011-06-23 CN CN 201110170049 patent/CN102276553B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1884269A (en) * | 2006-07-05 | 2006-12-27 | 浙江工业大学 | 2-[(2-methyl-4-hydroxy benzyl)azo]-1,3,4-thiadiazole and its preparation and use |
Non-Patent Citations (5)
| Title |
|---|
| 《华中师范大学学报（自然科学版）》 20110331 唐子龙，等 "一锅法"合成（芳氨基甲基）苯酚 63-67 1-2 第45卷, 第1期 * |
| 《精细化工中间体》 20100430 唐子龙，等 "一锅法"合成2-（氨基甲基）苯酚 22-25 1-2 第40卷, 第2期 * |
| 唐子龙，等: ""一锅法"合成（芳氨基甲基）苯酚", 《华中师范大学学报（自然科学版）》 * |
| 唐子龙，等: ""一锅法"合成2-（氨基甲基）苯酚", 《精细化工中间体》 * |
| 唐子龙，等: "N-1,3,4-噻二唑基取代水杨醛Schiff碱的合成与表征", 《精细化工中间体》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102757405A (en) * | 2012-07-25 | 2012-10-31 | 山东理工大学 | Vanilline derivative containing thiadiazole, preparation method and purpose thereof |
| CN102757405B (en) * | 2012-07-25 | 2014-04-16 | 山东理工大学 | Vanilline derivative containing thiadiazole, preparation method and purpose thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102276553B (en) | 2013-04-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| You et al. | Inhibition studies of Helicobacter pylori urease with Schiff base copper (II) complexes | |
| Yang et al. | Synthesis of novel (E)-2-(4-(1 H-1, 2, 4-triazol-1-yl) styryl)-4-(alkyl/arylmethyleneoxy) quinazoline derivatives as antimicrobial agents | |
| CN102838571B (en) | Andrographolide derivative containing gamma-subunit butenolide, synthetic method and application thereof | |
| Hong et al. | Three insensitive energetic co-crystals of 1-nitronaphthalene, with 2, 4, 6-trinitrotoluene (TNT), 2, 4, 6-trinitrophenol (picric acid) and D-mannitol hexanitrate (MHN) | |
| CN101544633B (en) | Synthesis technology for methyl thiadiazole formamide | |
| CN102276553B (en) | 2-((1,3,4- thiadiazolyl)aminomethyl) phenol compound with bactericidal activity | |
| CN102766124A (en) | Chromone-containing benzoyl hydrazone compound capable of suppressing growth of cyanobacteria | |
| Ünver et al. | Synthesis and antimicrobial evaluation of novel di-triazoles and 4-arylidene amino 4, 5 dihydro-1H-[1, 2, 4] triazole-5-one derivatives | |
| Küçükbay et al. | Synthesis and antimicrobial activities of some transition metal benzimidazole complexes | |
| Liao et al. | Design, synthesis and biological evaluation of soluble 2, 5-diketopiperazines derivatives as potential antifouling agents | |
| Rao et al. | Synthesis, structure analysis and cytotoxicity studies of novel unsymmetrically N, N′-substituted ureas from dehydroabietic acid | |
| CN102633741A (en) | Application of thiazole compounds in aspect of killing fresh water algae | |
| CN102250102A (en) | Alpha(beta)quinoline-oligopolycthylene glycol phthalocyanine zinc and preparation method thereof | |
| CN102850342B (en) | Oxdiazole compound containing thiadiazole, preparation method and applications thereof | |
| Su et al. | Synthesis and biological evaluation of novel sulfone derivatives containing 1, 3, 4-oxadiazole moiety | |
| Yusuf et al. | Synthesis and antimicrobial studies of new N, N′-[5, 5′-{2, 2′-(bis-alkoxy) bis (2, 1-phenylene)] bis (4-acetyl-4, 5-dihydro-1, 3, 4-thiadiazole-5, 2-diyl)] diacetamide | |
| CN103011279A (en) | Method for synthesizing spherical nano-zirconia by using detonation method in grain diameter controllable manner | |
| CN106083646B (en) | Different Korean pine acylhydrazone and preparation method and application | |
| Feng et al. | Synthesis and Insecticidal Evaluation of Novel N‐Pyridylpyrazolecarboxamides Containing Different Substituents in the ortho‐Position | |
| Shishkin et al. | Synthesis of N-(2-aminoethyl)-and N-(3-aminopropyl) cytisine | |
| Akhmetova et al. | Synthesis and fungicidal activity of alkyl (aryl)-substituted 1, 3, 4-thiadiazolidines | |
| CN106279028A (en) | 1,2 pair of (3,5 dinitro 1H pyrazoles 4 base) diazene potassium salt structure preparation method and performance | |
| Osyanin et al. | Synthesis of 9, 11-diamino-12 H-benzo [5, 6]-chromeno [2, 3-b] pyridine-10-carbonitriles | |
| Elizbarashvili et al. | Synthesis of macrocyclic polyazomethines | |
| Dong et al. | Synthesis and crystal structure of new heterocyclic compounds containing 1, 2, 3-triazole moiety |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20130410 Termination date: 20160623 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |