CN109535136A - 2- [4- (2- furyl)] pyrimidine radicals carbamide compounds and its preparation method and application - Google Patents
2- [4- (2- furyl)] pyrimidine radicals carbamide compounds and its preparation method and application Download PDFInfo
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- CN109535136A CN109535136A CN201811604672.8A CN201811604672A CN109535136A CN 109535136 A CN109535136 A CN 109535136A CN 201811604672 A CN201811604672 A CN 201811604672A CN 109535136 A CN109535136 A CN 109535136A
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- dehydrated alcohol
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- furyl
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- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- -1 methoxyl group Chemical group 0.000 claims abstract description 14
- 241000607479 Yersinia pestis Species 0.000 claims abstract description 9
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical class OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 7
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 4
- 125000001309 chloro group Chemical group Cl* 0.000 claims abstract description 4
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 4
- 125000001153 fluoro group Chemical group F* 0.000 claims abstract description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 4
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 34
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 31
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 29
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- 239000011259 mixed solution Substances 0.000 claims description 14
- 230000001580 bacterial effect Effects 0.000 claims description 12
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- 239000002808 molecular sieve Substances 0.000 claims description 8
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 239000000706 filtrate Substances 0.000 claims description 7
- 230000000855 fungicidal effect Effects 0.000 claims description 7
- 239000000417 fungicide Substances 0.000 claims description 7
- 239000005457 ice water Substances 0.000 claims description 7
- 239000000741 silica gel Substances 0.000 claims description 7
- 229910002027 silica gel Inorganic materials 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Natural products CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 claims description 6
- 238000001514 detection method Methods 0.000 claims description 6
- 201000010099 disease Diseases 0.000 claims description 6
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 claims description 6
- 239000002917 insecticide Substances 0.000 claims description 6
- 239000011541 reaction mixture Substances 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 5
- BUZYGTVTZYSBCU-UHFFFAOYSA-N 1-(4-chlorophenyl)ethanone Chemical group CC(=O)C1=CC=C(Cl)C=C1 BUZYGTVTZYSBCU-UHFFFAOYSA-N 0.000 claims description 4
- GNKZMNRKLCTJAY-UHFFFAOYSA-N 4'-Methylacetophenone Chemical compound CC(=O)C1=CC=C(C)C=C1 GNKZMNRKLCTJAY-UHFFFAOYSA-N 0.000 claims description 4
- OUDFNZMQXZILJD-UHFFFAOYSA-N 5-methyl-2-furaldehyde Chemical compound CC1=CC=C(C=O)O1 OUDFNZMQXZILJD-UHFFFAOYSA-N 0.000 claims description 4
- 150000008062 acetophenones Chemical class 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 4
- 244000291564 Allium cepa Species 0.000 claims description 3
- 235000002732 Allium cepa var. cepa Nutrition 0.000 claims description 3
- 241000207199 Citrus Species 0.000 claims description 3
- 244000241257 Cucumis melo Species 0.000 claims description 3
- 235000015510 Cucumis melo subsp melo Nutrition 0.000 claims description 3
- 244000061456 Solanum tuberosum Species 0.000 claims description 3
- 235000002595 Solanum tuberosum Nutrition 0.000 claims description 3
- 241000254113 Tribolium castaneum Species 0.000 claims description 3
- 240000008042 Zea mays Species 0.000 claims description 3
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 claims description 3
- 235000002017 Zea mays subsp mays Nutrition 0.000 claims description 3
- FJJCIZWZNKZHII-UHFFFAOYSA-N [4,6-bis(cyanoamino)-1,3,5-triazin-2-yl]cyanamide Chemical compound N#CNC1=NC(NC#N)=NC(NC#N)=N1 FJJCIZWZNKZHII-UHFFFAOYSA-N 0.000 claims description 3
- 235000020971 citrus fruits Nutrition 0.000 claims description 3
- 235000005822 corn Nutrition 0.000 claims description 3
- 235000013399 edible fruits Nutrition 0.000 claims description 3
- 125000002941 2-furyl group Chemical group O1C([*])=C([H])C([H])=C1[H] 0.000 claims description 2
- 241000254154 Sitophilus zeamais Species 0.000 claims description 2
- 238000007689 inspection Methods 0.000 claims 1
- 238000002156 mixing Methods 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 41
- 241000894006 Bacteria Species 0.000 abstract description 11
- 230000001717 pathogenic effect Effects 0.000 abstract description 6
- 150000002240 furans Chemical class 0.000 abstract description 5
- 239000000575 pesticide Substances 0.000 abstract description 5
- 230000002401 inhibitory effect Effects 0.000 abstract description 4
- 238000003860 storage Methods 0.000 abstract description 4
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 abstract description 3
- 150000001408 amides Chemical class 0.000 abstract description 2
- 231100000331 toxic Toxicity 0.000 abstract 1
- 230000002588 toxic effect Effects 0.000 abstract 1
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 20
- 239000001257 hydrogen Substances 0.000 description 11
- 229910052739 hydrogen Inorganic materials 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 10
- 238000001819 mass spectrum Methods 0.000 description 10
- NTPLXRHDUXRPNE-UHFFFAOYSA-N 4-methoxyacetophenone Chemical compound COC1=CC=C(C(C)=O)C=C1 NTPLXRHDUXRPNE-UHFFFAOYSA-N 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- 241000196324 Embryophyta Species 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 239000003814 drug Substances 0.000 description 4
- 239000012265 solid product Substances 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 230000003385 bacteriostatic effect Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000001963 growth medium Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 230000001376 precipitating effect Effects 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 230000003595 spectral effect Effects 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 239000001888 Peptone Substances 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 235000006708 antioxidants Nutrition 0.000 description 2
- 235000015278 beef Nutrition 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 230000003013 cytotoxicity Effects 0.000 description 2
- 231100000135 cytotoxicity Toxicity 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 238000004134 energy conservation Methods 0.000 description 2
- 150000002391 heterocyclic compounds Chemical class 0.000 description 2
- 231100000053 low toxicity Toxicity 0.000 description 2
- 230000008635 plant growth Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- KRIOVPPHQSLHCZ-UHFFFAOYSA-N propiophenone Chemical compound CCC(=O)C1=CC=CC=C1 KRIOVPPHQSLHCZ-UHFFFAOYSA-N 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000012488 sample solution Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 230000001954 sterilising effect Effects 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- 238000009333 weeding Methods 0.000 description 2
- SEPPVOUBHWNCAW-FNORWQNLSA-N (E)-4-oxonon-2-enal Chemical compound CCCCCC(=O)\C=C\C=O SEPPVOUBHWNCAW-FNORWQNLSA-N 0.000 description 1
- LLBZPESJRQGYMB-UHFFFAOYSA-N 4-one Natural products O1C(C(=O)CC)CC(C)C11C2(C)CCC(C3(C)C(C(C)(CO)C(OC4C(C(O)C(O)C(COC5C(C(O)C(O)CO5)OC5C(C(OC6C(C(O)C(O)C(CO)O6)O)C(O)C(CO)O5)OC5C(C(O)C(O)C(C)O5)O)O4)O)CC3)CC3)=C3C2(C)CC1 LLBZPESJRQGYMB-UHFFFAOYSA-N 0.000 description 1
- 206010059866 Drug resistance Diseases 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 241000322338 Loeseliastrum Species 0.000 description 1
- 206010027146 Melanoderma Diseases 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 241000700605 Viruses Species 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000001093 anti-cancer Effects 0.000 description 1
- 230000003110 anti-inflammatory effect Effects 0.000 description 1
- 230000000259 anti-tumor effect Effects 0.000 description 1
- 230000000840 anti-viral effect Effects 0.000 description 1
- 238000004500 asepsis Methods 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000010431 corundum Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229960004756 ethanol Drugs 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000012010 growth Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000003845 household chemical Substances 0.000 description 1
- 230000000749 insecticidal effect Effects 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 239000002068 microbial inoculum Substances 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 150000003230 pyrimidines Chemical class 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
- C07D405/04—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
- A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
- A01N47/36—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the group >N—CO—N< directly attached to at least one heterocyclic ring; Thio analogues thereof
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
The present invention provides a kind of 2- [4- (2- furyl)] pyrimidine radicals carbamide compounds and its preparation method and application, general structure are as follows:R in general formula1For fluorine atom, chlorine atom, bromine atom, iodine atom, methyl, methoxyl group, R2For hydrogen atom, bromine atom, methyl, methylol.Furan nucleus and amide are introduced into the molecular structure of pyrimidine by compound provided by the present application, have synthesized some 2- [4- (2- furyl)] pyrimidine radicals carbamide compounds.Their structures are simple, have preferable toxic effect to storage pest, also have preferable inhibitory activity to plant pathogenetic bacteria, will lay a good foundation for the initiative of novel pesticide.
Description
Technical field
The present invention relates to technical field of pesticide more particularly to a kind of 2- [4- (2- furyl)] pyrimidine radicals carbamide compounds and
Preparation method and application.
Background technique
Amides compound has extensive bioactivity, including sterilization, anti-oxidant, plant growth regulating etc..Therefore, exist
In the past few decades, it is had made extensive and intensive studies, it was found that many new and effective compounds, but also constantly
There is structure novel, mode of action uniqueness, has excellent performance, is efficient to harmful organism, is safe to non-target organism, easily dropping in the environment
It solves and catabolite reports the kind of human health and ecological environment security.
Pyrimidine is a kind of very important heterocyclic compound, is widely used in the fields such as medicine, pesticide, household chemicals.Greatly
Quantity research shows that such compound has preferable bioactivity, such as desinsection, sterilization, mite killing, weeding, plant growth regulating, resists
Virus, anticancer, anti-oxidant, anti-inflammatory etc..Since pyrimidines have efficiently, to people and animals' low toxicity, mode of action uniqueness, nocuousness
Biology is not likely to produce the advantages that drug resistance, and therefore, design, synthesis and the bioactivity research of molecular structure are heterocyclic compounds
Constantly there are structure novel, simple, the good compound appearance of bioactivity in a very active field in research.
It is well known that furan nucleus is an electron rich system, it is easy to form intermolecular hydrogen bonding, therefore, one with a variety of biological enzyme
It is either natural or artificial synthesized that all there is wide spectrum biological activity a bit containing the compound of furan nucleus, for example, antibacterial,
Antiviral and antitumor, desinsection and weeding etc..Meanwhile these compounds usually all have efficient, low toxicity, pacify to non-target organism
Entirely, easy degradation, harmful organism do not allow the features such as being also easy to produce resistance in the environment, so, in the research and development process of pesticide
In, the compound containing furan nucleus shows increasingly important role.
Up to the present, 2- [4- (2- furyl)] pyrimidine radicals carbamide compounds be yet there are no as agricultural insecticide and killed
The report that microbial inoculum uses.
Summary of the invention
The purpose of the present invention is to provide it is a kind of new be used as agricultural insecticide, fungicide compound and they
Preparation method.
A kind of 2- [4- (2- furyl)] pyrimidine radicals carbamide compounds, general structure are as follows:
R in logical formula (I)1For fluorine atom, chlorine atom, bromine atom, iodine atom, methyl, methoxyl group, R2It is former for hydrogen atom, bromine
Son, methyl, methylol.
A kind of preparation method of 2- [4- (2- furyl)] pyrimidine radicals carbamide compounds: substituted acetophenone is dissolved in anhydrous
In ethyl alcohol, then 10%NaOH solution is added thereto, under ice bath stirring, by the mixed liquor or 5- first of furfural and dehydrated alcohol
The mixed liquor of base furfural and dehydrated alcohol is slowly instilled in above-mentioned mixed solution with constant pressure funnel, is reacted at 0-5 DEG C, and
Check whether reaction is completed with thin layer silica gel plate (TLC).After the reaction was completed, 13X molecular sieve is added into reaction mixture, is used in combination
Constant pressure funnel slowly instills the mixed solution of urea sulfuric acid amidine and dehydrated alcohol into mixture, reacts at 40-50 DEG C,
Whether completed with TLC detection reaction.After the reaction was completed, it filters, a large amount of ice water is added into filtrate, adjusted with 10% hydrochloric acid solution
PH has Precipitation, filters, wash to neutrality, then is recrystallized with dehydrated alcohol to get the target compound is arrived.
Further, method as described above, the substituted acetophenone are 4- chloro-acetophenone, 4- methoxyacetophenone, 4-
One of methyl acetophenone.
Further, method as described above, the 13X molecular sieve are 40-60 mesh.
A kind of 2- [4- (2- furyl)] application of the pyrimidine radicals carbamide compounds as agricultural insecticide or fungicide.
Further, application as described above, the pest that the insecticide is killed are in sitophilus zea-mais, Gu Du and red flour beetle
It is one or more.
Further, application as described above, it is bacillary that the fungicide is able to suppress corn bacterial brown spot, rape
One of black spot, citrus bacterial canker disease, blakleg of potato, onion bulb rot disease, melon bacterial fruit blotch are a variety of.
The utility model has the advantages that
Furan nucleus and amide are introduced into the molecular structure of pyrimidine by the present invention, and it is phonetic to have synthesized some 2- [4- (2- furyl)]
Piperidinyl carbamide compounds.Their structures are simple, superior activity, will lay a good foundation for the initiative of novel pesticide.
The synthesis process of the compound of logical formula (I) is simple, and the method for using " treating different things alike ", i.e., be not by traditional method
Intermediate is separated to the reaction for carrying out next step again, but directly carries out the reaction of next step, which reduces operations
Step improves reaction efficiency, is beneficial to energy conservation consumption reduction.The compound of logical formula (I) to storage pest and plant pathogenetic bacteria all
There is preferable control efficiency, is had not been reported in the desinsection and fungicide being currently known.
Detailed description of the invention
Fig. 1 is the hydrogen spectrogram for the compound that embodiment 1 is prepared；
Fig. 2 is the carbon spectrogram for the compound that embodiment 1 is prepared；
Fig. 3 is the high resolution mass spectrum figure for the compound that embodiment 1 is prepared；
Fig. 4 is the hydrogen spectrogram for the compound that embodiment 2 is prepared；
Fig. 5 is the carbon spectrogram for the compound that embodiment 2 is prepared；
Fig. 6 is the high resolution mass spectrum figure for the compound that embodiment 2 is prepared；
Fig. 7 is the hydrogen spectrogram for the compound that embodiment 3 is prepared；
Fig. 8 is the carbon spectrogram for the compound that embodiment 3 is prepared；
Fig. 9 is the high resolution mass spectrum figure for the compound that embodiment 3 is prepared；
Figure 10 is the hydrogen spectrogram for the compound that embodiment 4 is prepared；
Figure 11 is the carbon spectrogram for the compound that embodiment 4 is prepared；
Figure 12 is the high resolution mass spectrum figure for the compound that embodiment 4 is prepared；
Figure 13 is the hydrogen spectrogram for the compound that embodiment 5 is prepared；
Figure 14 is the carbon spectrogram for the compound that embodiment 5 is prepared；
Figure 15 is the high resolution mass spectrum figure for the compound that embodiment 5 is prepared.
Specific embodiment
To make the object, technical solutions and advantages of the present invention clearer, the technical solution below in the present invention carries out clear
Chu is fully described by, it is clear that described embodiments are some of the embodiments of the present invention, instead of all the embodiments.It is based on
Embodiment in the present invention, it is obtained by those of ordinary skill in the art without making creative efforts every other
Embodiment shall fall within the protection scope of the present invention.
The present invention provides a kind of compound with desinsection and bacteriostatic activity, general structure is as follows:
R in logical formula (I)1For fluorine atom, chlorine atom, bromine atom, iodine atom, methyl, methoxyl group, R2It is former for hydrogen atom, bromine
Son, methyl, methylol.
General formula is the key reaction equation in the preparation of compounds of (I) are as follows:
R in formula1、R2Meaning be same as above.
The synthesis process of the compound of logical formula (I) is simple, and the method for using " treating different things alike ", i.e., be not by traditional method
Intermediate is separated to the reaction for carrying out next step again, but directly carries out the reaction of next step, which reduces operations
Step improves reaction efficiency, is beneficial to energy conservation consumption reduction.The compound of logical formula (I) to storage pest and plant pathogenetic bacteria all
There is preferable control efficiency, is had not been reported in the desinsection and fungicide being currently known.
Embodiment 1:
CompoundPreparation
0.02mol 4- methoxyacetophenone is dissolved in 20mL dehydrated alcohol, then 15mL 10% is added thereto
NaOH solution.Under ice bath stirring, the mixed liquor of 0.02mol furfural and 20mL dehydrated alcohol is slowly dripped with constant pressure funnel
Enter in above-mentioned mixed solution, reacted at 0-5 DEG C, and checks whether reaction is completed with thin layer silica gel plate (TLC).Reaction is completed
Afterwards, 2 grams of 13X molecular sieves (40-60 mesh) are added into reaction mixture, and are slowly instilled into mixture with constant pressure funnel
Whether the mixed solution of 0.02mol urea sulfuric acid amidine and 20mL dehydrated alcohol reacts at 40-50 DEG C, complete with TLC detection reaction
At.After the reaction was completed, it filters, a large amount of ice water is added into filtrate, adjust pH to neutrality with 10% hydrochloric acid solution, there is precipitating to analyse
Out, it filters, washing, then is recrystallized with dehydrated alcohol to get pale yellow powder shape solid product, yield 81% is arrived.Product
Spectral data is as follows:
1H NMR(400MHz,DMSO-d6) δ (ppm): 9.56 (1H, s), 8.71 (1H, s), 8.19 (2H, d, J=
8.8Hz), 8.02 (1H, d, J=0.8Hz), 7.84 (1H, s), 7.52 (1H, d, J=3.6Hz), 7.16 (1H, s), 7.12 (2H,
D, J=8.8Hz), 6.78 (1H, dd, J1=3.6Hz, J2=3.6Hz), 3.86 (3H, s)；13C NMR(100MHz,DMSO-d6)δ
(ppm):164.82,162.45,158.96,155.81,155.32,151.29,146.73,129.31,128.62,114.79,
113.94,113.29,103.39,55.91；HRMS(ESI)m/z:Calcd for C16H14N4O3[M+Na]+:333.0959,
Found:333.0939.
Hydrogen spectrogram, carbon spectrogram, the high resolution mass spectrum figure of product are as shown in Figs. 1-3.
Embodiment 2:
CompoundPreparation
0.02mol 4- chloro-acetophenone is dissolved in 20mL dehydrated alcohol, then addition 15mL10%NaOH is molten thereto
Liquid.Under ice bath stirring, slowly with constant pressure funnel by the mixed liquor of 0.02mol 5 methyl furfural and 20mL dehydrated alcohol
It instills in above-mentioned mixed solution, is reacted at 0-5 DEG C, and check whether reaction is completed with thin layer silica gel plate (TLC).Reaction is completed
Afterwards, 2 grams of 13X molecular sieves (40-60 mesh) are added into reaction mixture, and are slowly instilled into mixture with constant pressure funnel
Whether the mixed solution of 0.02mol urea sulfuric acid amidine and 20mL dehydrated alcohol reacts at 40-50 DEG C, complete with TLC detection reaction
At.After the reaction was completed, it filters, a large amount of ice water is added into filtrate, adjust pH to neutrality with 10% hydrochloric acid solution, there is precipitating to analyse
Out, it filters, washing, then is recrystallized with dehydrated alcohol to get white needle-like crystals product, yield 86% is arrived.The wave spectrum of product
Data are as follows:
1H NMR(400MHz,DMSO-d6) δ (ppm): 9.57 (1H, s), 8.72 (1H, s), 8.20 (2H, d, J=
8.8Hz), 8.03 (1H, s), 7.85 (1H, s), 7.53 (1H, s), 7.13 (2H, d, J=8.8Hz), 6.80 (1H, s), 2.43
(3H,s)；13C NMR(100MHz,DMSO-d6)δ(ppm):164.26,162.04,155.27,150.71,138.22,
133.44,132.16,131.36,128.91,127.29,114.08,109.38,100.05,14.09；HRMS(ESI)m/z:
Calcd for C16H13N4O2Cl[M+H]+:322.0805,Found:322.0836.
Hydrogen spectrogram, carbon spectrogram, the high resolution mass spectrum figure of product are as Figure 4-Figure 6.
Embodiment 3:
CompoundPreparation
0.02mol 4- methyl acetophenone is dissolved in 20mL dehydrated alcohol, then addition 15mL10%NaOH is molten thereto
Liquid.Under ice bath stirring, slowly with constant pressure funnel by the mixed liquor of 0.02mol 5 methyl furfural and 20mL dehydrated alcohol
It instills in above-mentioned mixed solution, is reacted at 0-5 DEG C, and check whether reaction is completed with thin layer silica gel plate (TLC).Reaction is completed
Afterwards, 2 grams of 13X molecular sieves (40-60 mesh) are added into reaction mixture, and are slowly instilled into mixture with constant pressure funnel
Whether the mixed solution of 0.02mol urea sulfuric acid amidine and 20mL dehydrated alcohol reacts at 40-50 DEG C, complete with TLC detection reaction
At.After the reaction was completed, it filters, a large amount of ice water is added into filtrate, adjust pH to neutrality with 10% hydrochloric acid solution, there is precipitating to analyse
Out, it filters, washing, then is recrystallized with dehydrated alcohol to get white solid product, yield 91% is arrived.The spectral data of product
It is as follows:
1H NMR(400MHz,DMSO-d6) δ (ppm): 9.57 (1H, s), 8.72 (1H, s), 8.20 (2H, d, J=
8.8Hz), 8.04 (1H, s), 7.85 (1H, s), 7.53 (1H, d, J=3.6Hz), 7.13 (2H, d, J=8.8Hz), 6.80 (1H,
dd,J1=3.6Hz, J2=3.6Hz), 2.44 (3H, s), 2.41 (3H, s)；13C NMR(100MHz,DMSO-d6)δ(ppm):
165.82,163.45,159.96,156.81,156.32,152.29,147.73,130.31,129.62,115.79,114.94,
114.29,104.39,21.23,14.01；HRMS(ESI)m/z:Calcd for C17H16N4O2[M+H]+:309.1351,
Found:309.1343.
Hydrogen spectrogram, carbon spectrogram, the high resolution mass spectrum figure of product are as Figure 7-9.
Embodiment 4:
CompoundPreparation
0.02mol 4- methoxyacetophenone is dissolved in 20mL dehydrated alcohol, then 15mL 10% is added thereto
NaOH solution.Under ice bath stirring, the mixed liquor of 0.02mol 5 methyl furfural and 20mL dehydrated alcohol is leaked with constant pressure addition
Bucket slowly instills in above-mentioned mixed solution, reacts at 0-5 DEG C, and checks whether reaction is completed with thin layer silica gel plate (TLC).Instead
After the completion of answering, 2 grams of 13X molecular sieves (40-60 mesh) are added into reaction mixture, and with constant pressure funnel slowly to mixture
The middle mixed solution for instilling 0.02mol urea sulfuric acid amidine and 20mL dehydrated alcohol, reacts at 40-50 DEG C, is detected and is reacted with TLC
Whether complete.After the reaction was completed, it filters, a large amount of ice water is added into filtrate, adjust pH to neutrality with 10% hydrochloric acid solution, there have to be heavy
Precipitation goes out, and filters, washing, then is recrystallized with dehydrated alcohol to get gray solid product, yield 83% is arrived.The wave spectrum of product
Data are as follows:
1H NMR(400MHz,DMSO-d6) δ (ppm): 9.56 (1H, s), 8.71 (1H, s), 8.19 (2H, d, J=
8.8Hz), 8.03 (1H, s), 7.84 (1H, s), 7.52 (1H, d, J=3.6Hz), 7.16 (1H, s), 7.12 (2H, d, J=
8.8Hz),3.87(3H,s),2.40(3H,s)；13C NMR(100MHz,DMSO-d6)δ(ppm):162.76,161.33,
155.45,154.90,154.78,153.29,142.83,131.40,128.27,114.37,107.86,106.35,104.95,
56.30,14.76；HRMS(ESI)m/z:Calcd for C17H16N4O3[M+Na]+:347.1117,Found:347.1106.
The hydrogen spectrogram of product, carbon spectrogram, high resolution mass spectrum figure are as shown in figs. 10-12.
Embodiment 5:
CompoundPreparation
0.02mol 4- chloro-acetophenone is dissolved in 20mL dehydrated alcohol, then addition 15mL10%NaOH is molten thereto
Liquid.Under ice bath stirring, the mixed liquor of 0.02mol furfural and 20mL dehydrated alcohol is slowly instilled with constant pressure funnel above-mentioned
It in mixed solution, is reacted at 0-5 DEG C, and checks whether reaction is completed with thin layer silica gel plate (TLC).After the reaction was completed, to anti-
2 grams of 13X molecular sieves (40-60 mesh) of addition in mixture are answered, and slowly instill 0.02mol into mixture with constant pressure funnel
Whether the mixed solution of urea sulfuric acid amidine and 20mL dehydrated alcohol reacts at 40-50 DEG C, completed with TLC detection reaction.Reaction
After the completion, it filters, a large amount of ice water is added into filtrate, with 10% hydrochloric acid solution adjusting pH to neutrality, there is Precipitation, filter,
Washing, then recrystallized with dehydrated alcohol to get pale yellow powder shape solid product, yield 90% is arrived.The spectral data of product
It is as follows:
1H NMR(400MHz,DMSO-d6)δ(ppm):9.64(1H,s),8.64(1H,s),8.28(2H,dd,J1=
8.4Hz,J2=8.4Hz), 8.03 (1H, s), 7.90 (1H, s), 7.55 (1H, d, J=3.2Hz), 7.41 (2H, t, J=
8.8Hz),7.18(1H,s),6.79(1H,dd,J1=3.2Hz, J2=3.2Hz)；13C NMR(100MHz,DMSO-d6)δ
(ppm):164.19,159.00,156.13,155.24,151.12,146.92,130.15,130.06,116.50,116.28,
114.33,113.35,104.14；HRMS(ESI)m/z:Calcd for C15H11N4O2Cl[M+Na]+:337.0464,Found:
337.0458.
The hydrogen spectrogram of product, carbon spectrogram, high resolution mass spectrum figure are as illustrated in figs. 13-15.
Embodiment 6: the measurement of the compounds of this invention insecticidal activity
(1) test pest
Corundum Sitophilusspp. imago, Gu Du adult and red flour beetle adult, they are the indoor sensitive strain for many generations raised throughout the year.
(2) measuring method
Medicine method is mixed using feed: untested compound and wheatfeed are uniformly mixed by certain dosage.100 grams are weighed to mix
Medicine feed puts into test pest 30 into each bottle in 500mL wide-mouth bottle, wraps up bottleneck with calico, then place it in
Temperature is 28~30 DEG C, continues to raise in the insectary that relative humidity is 70~80%, while the feed not mix medicine is blank
Control.Death condition is recorded after 14 days, each experiment is repeated 3 times, and calculates corrected mortality with following equation:
(3) experimental result
The desinsection of the compounds of this invention the results are shown in Table 1.
Cytotoxicity of 1 the compounds of this invention of table to storage pest
a: duplicate average value three times.
There is preferable cytotoxicity to these pests from the compounds of this invention known to upper table 1.
Embodiment 7: the measurement of the compounds of this invention bacteriostatic activity
(1) test plant pathogenetic bacteria
Corn bacterial brown spot, rape bacterial black rot, citrus bacterial canker disease, blakleg of potato, onion bulb are rotten
Rotten disease, melon bacterial fruit blotch.
(2) measuring method
(a) activation of strain: beef extract-peptone culture medium slant, 37 DEG C of mistakes will be inoculated in for the bacterium bacterial strain of examination
Night culture.
(b) preparation of bacteria suspension: in the conical flask equipped with 100mL beef extract-peptone fluid nutrient medium, it is inoculated with a ring
The strains tested activated, in 37 DEG C of culture 18h, after obtaining initial bacteria suspension, then it is dilute using gradient with sterile saline
Interpretation of the law is made into debita spissitudo (106~107CFU/mL bacteria suspension) is spare.
(c) measurement of minimum inhibitory concentration (MIC): test compound is dissolved in dimethyl sulfoxide, then is spat with containing 0.1%
The sterile saline of temperature -80, the solution of various concentration is diluted to using doubling dilution, is uniformly mixed.After taking dilution
Sample solution 1mL, be added in sterilized 19mL culture medium, be uniformly mixed, plate is made.After culture medium solidification, use
It is 10 that above-mentioned concentration, which is added, in rubbing method6The 200 μ L of bacteria suspension of CFU/mL observes bacterial growth feelings in 37 DEG C of 16~18h of culture
Condition, using the concentration that integral asepsis is grown as the MIC value of test sample solution, meanwhile, with corresponding molten without test compound
Liquid is blank control.
(3) experimental result
The bacteriostatic activity of the compounds of this invention is shown in Table 2.
Inhibitory activity of 2 the compounds of this invention of table to plant pathogenetic bacteria
There is preferable inhibitory effect to these plant pathogenetic bacterias from the compounds of this invention known to upper table 2.
Finally, it should be noted that the above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations；Although
Present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that: it still may be used
To modify the technical solutions described in the foregoing embodiments or equivalent replacement of some of the technical features；
And these are modified or replaceed, technical solution of various embodiments of the present invention that it does not separate the essence of the corresponding technical solution spirit and
Range.
Claims (7)
1. a kind of 2- [4- (2- furyl)] pyrimidine radicals carbamide compounds, which is characterized in that its general structure is as follows:
R in logical formula (I)1For fluorine atom, chlorine atom, bromine atom, iodine atom, methyl, methoxyl group, R2For hydrogen atom, bromine atom, first
Base, methylol.
2. a kind of preparation method of 2- [4- (2- furyl)] pyrimidine radicals carbamide compounds, it is characterised in that: by substituted acetophenone
It is dissolved in dehydrated alcohol, then 10%NaOH solution is added thereto, under ice bath stirring, by the mixing of furfural and dehydrated alcohol
The mixed liquor of liquid or 5 methyl furfural and dehydrated alcohol is slowly instilled in above-mentioned mixed solution with constant pressure funnel, in 0-5
It reacts at DEG C, and whether is completed with thin layer silica gel plate inspection reaction.After the reaction was completed, 13X molecule is added into reaction mixture
It sieves, and slowly instills the mixed solution of urea sulfuric acid amidine and dehydrated alcohol into mixture with constant pressure funnel, at 40-50 DEG C
Whether lower reaction is completed with TLC detection reaction.After the reaction was completed, it filters, a large amount of ice water is added into filtrate, with 10% hydrochloric acid
Solution adjusts pH to be had Precipitation, filters, wash to neutrality, then is recrystallized with dehydrated alcohol to get the target chemical combination is arrived
Object.
3. according to the method described in claim 2, it is characterized in that, the substituted acetophenone is 4- chloro-acetophenone, 4- methoxyl group
One of acetophenone, 4- methyl acetophenone.
4. according to the method described in claim 2, it is characterized in that, the 13X molecular sieve is 40-60 mesh.
5. a kind of 2- [4- (2- furyl)] application of the pyrimidine radicals carbamide compounds as agricultural insecticide or fungicide.
6. application according to claim 5, the pest that the insecticide is killed is in sitophilus zea-mais, Gu Du and red flour beetle
It is one or more.
7. application according to claim 5, it is bacillary black that the fungicide is able to suppress corn bacterial brown spot, rape
One of pinta, citrus bacterial canker disease, blakleg of potato, onion bulb rot disease, melon bacterial fruit blotch are a variety of.
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