CN114621121A - Preparation method of camphor sulfonyl hydrazine compound, product and application thereof - Google Patents
Preparation method of camphor sulfonyl hydrazine compound, product and application thereof Download PDFInfo
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- CN114621121A CN114621121A CN202210264700.6A CN202210264700A CN114621121A CN 114621121 A CN114621121 A CN 114621121A CN 202210264700 A CN202210264700 A CN 202210264700A CN 114621121 A CN114621121 A CN 114621121A
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- Prior art keywords
- camphorsulfonyl
- chloride
- compound
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- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- -1 camphor sulfonyl hydrazine compound Chemical class 0.000 title claims description 11
- 150000001875 compounds Chemical class 0.000 claims abstract description 72
- 241000723346 Cinnamomum camphora Species 0.000 claims abstract description 27
- 229930008380 camphor Natural products 0.000 claims abstract description 25
- 229960000846 camphor Drugs 0.000 claims abstract description 25
- 241000196324 Embryophyta Species 0.000 claims abstract description 12
- 241000233866 Fungi Species 0.000 claims abstract description 11
- 241000233616 Phytophthora capsici Species 0.000 claims abstract description 8
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical class CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 84
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical class CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 56
- BGABKEVTHIJBIW-XVKPBYJWSA-N [(1s,4r)-7,7-dimethyl-3-oxo-4-bicyclo[2.2.1]heptanyl]methanesulfonyl chloride Chemical compound C1C[C@]2(CS(Cl)(=O)=O)C(=O)C[C@H]1C2(C)C BGABKEVTHIJBIW-XVKPBYJWSA-N 0.000 claims description 37
- 238000006243 chemical reaction Methods 0.000 claims description 30
- 238000001816 cooling Methods 0.000 claims description 28
- 239000007787 solid Substances 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 16
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 10
- JOVOSQBPPZZESK-UHFFFAOYSA-N phenylhydrazine hydrochloride Chemical class Cl.NNC1=CC=CC=C1 JOVOSQBPPZZESK-UHFFFAOYSA-N 0.000 claims description 8
- 229940038531 phenylhydrazine hydrochloride Drugs 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- FYSSYOCJFZSKNW-UHFFFAOYSA-N hydron;naphthalen-1-ylhydrazine;chloride Chemical compound [Cl-].C1=CC=C2C(N[NH3+])=CC=CC2=C1 FYSSYOCJFZSKNW-UHFFFAOYSA-N 0.000 claims description 5
- 241000223195 Fusarium graminearum Species 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 238000003786 synthesis reaction Methods 0.000 claims description 3
- 230000002194 synthesizing effect Effects 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 2
- 150000002429 hydrazines Chemical class 0.000 claims 2
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- 235000005663 Carya cathayensis Nutrition 0.000 claims 1
- 239000000758 substrate Substances 0.000 claims 1
- 241000209140 Triticum Species 0.000 abstract description 11
- 235000021307 Triticum Nutrition 0.000 abstract description 11
- 206010039509 Scab Diseases 0.000 abstract description 9
- 241000899834 Obovaria olivaria Species 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 5
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 127
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 76
- 238000005406 washing Methods 0.000 description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 31
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 24
- 239000012044 organic layer Substances 0.000 description 22
- 239000002994 raw material Substances 0.000 description 21
- 239000012043 crude product Substances 0.000 description 20
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 19
- 238000005160 1H NMR spectroscopy Methods 0.000 description 19
- 238000004587 chromatography analysis Methods 0.000 description 18
- 238000004440 column chromatography Methods 0.000 description 18
- 238000001035 drying Methods 0.000 description 18
- 238000012544 monitoring process Methods 0.000 description 18
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 17
- DSSYKIVIOFKYAU-XCBNKYQSSA-N (R)-camphor Chemical compound C1C[C@@]2(C)C(=O)C[C@@H]1C2(C)C DSSYKIVIOFKYAU-XCBNKYQSSA-N 0.000 description 12
- 238000000967 suction filtration Methods 0.000 description 12
- 239000000543 intermediate Substances 0.000 description 8
- 244000061456 Solanum tuberosum Species 0.000 description 7
- 235000002595 Solanum tuberosum Nutrition 0.000 description 7
- 238000001914 filtration Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 230000005764 inhibitory process Effects 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000001963 growth medium Substances 0.000 description 5
- 239000013641 positive control Substances 0.000 description 5
- 235000012015 potatoes Nutrition 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000005788 Fluxapyroxad Substances 0.000 description 4
- 239000003814 drug Substances 0.000 description 4
- SXSGXWCSHSVPGB-UHFFFAOYSA-N fluxapyroxad Chemical compound FC(F)C1=NN(C)C=C1C(=O)NC1=CC=CC=C1C1=CC(F)=C(F)C(F)=C1 SXSGXWCSHSVPGB-UHFFFAOYSA-N 0.000 description 4
- 230000002401 inhibitory effect Effects 0.000 description 4
- 229920001817 Agar Polymers 0.000 description 3
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 3
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 3
- 239000008272 agar Substances 0.000 description 3
- 230000000844 anti-bacterial effect Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 201000010099 disease Diseases 0.000 description 3
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000008103 glucose Substances 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 3
- 229940085790 synthetic camphor Drugs 0.000 description 3
- QELCWIMDZKOJBU-UHFFFAOYSA-N (2-chloro-4-fluorophenyl)hydrazine;hydrochloride Chemical compound [Cl-].[NH3+]NC1=CC=C(F)C=C1Cl QELCWIMDZKOJBU-UHFFFAOYSA-N 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
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- 238000005520 cutting process Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000004720 fertilization Effects 0.000 description 2
- 239000002674 ointment Substances 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- 230000001954 sterilising effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- VFZYLSYYMHFPSY-UHFFFAOYSA-N (2-fluoroanilino)azanium;chloride Chemical compound Cl.NNC1=CC=CC=C1F VFZYLSYYMHFPSY-UHFFFAOYSA-N 0.000 description 1
- CRRIAWUJYMLJOE-UHFFFAOYSA-N (3-chlorophenyl)hydrazine;hydron;chloride Chemical compound Cl.NNC1=CC=CC(Cl)=C1 CRRIAWUJYMLJOE-UHFFFAOYSA-N 0.000 description 1
- SKVGLOFWEJFQKU-UHFFFAOYSA-N (3-fluorophenyl)hydrazine;hydron;chloride Chemical compound Cl.NNC1=CC=CC(F)=C1 SKVGLOFWEJFQKU-UHFFFAOYSA-N 0.000 description 1
- RGGOWBBBHWTTRE-UHFFFAOYSA-N (4-bromophenyl)hydrazine;hydron;chloride Chemical compound Cl.NNC1=CC=C(Br)C=C1 RGGOWBBBHWTTRE-UHFFFAOYSA-N 0.000 description 1
- YQVZREHUWCCHHX-UHFFFAOYSA-N (4-chlorophenyl)hydrazine;hydron;chloride Chemical compound Cl.NNC1=CC=C(Cl)C=C1 YQVZREHUWCCHHX-UHFFFAOYSA-N 0.000 description 1
- FEKUXLUOKFSMRO-UHFFFAOYSA-N (4-fluorophenyl)hydrazine;hydron;chloride Chemical compound Cl.NNC1=CC=C(F)C=C1 FEKUXLUOKFSMRO-UHFFFAOYSA-N 0.000 description 1
- PBGQZFXOUDOZCB-UHFFFAOYSA-N (4-iodophenyl)hydrazine;hydrochloride Chemical compound [Cl-].[NH3+]NC1=CC=C(I)C=C1 PBGQZFXOUDOZCB-UHFFFAOYSA-N 0.000 description 1
- MIOPJNTWMNEORI-GMSGAONNSA-N (S)-camphorsulfonic acid Chemical compound C1C[C@@]2(CS(O)(=O)=O)C(=O)C[C@@H]1C2(C)C MIOPJNTWMNEORI-GMSGAONNSA-N 0.000 description 1
- DQXKOHDUMJLXKH-PHEQNACWSA-N (e)-n-[2-[2-[[(e)-oct-2-enoyl]amino]ethyldisulfanyl]ethyl]oct-2-enamide Chemical compound CCCCC\C=C\C(=O)NCCSSCCNC(=O)\C=C\CCCCC DQXKOHDUMJLXKH-PHEQNACWSA-N 0.000 description 1
- ZDCGBGBQRTYDFC-UHFFFAOYSA-N (pyridin-2-ylamino)azanium;chloride Chemical compound Cl.NNC1=CC=CC=N1 ZDCGBGBQRTYDFC-UHFFFAOYSA-N 0.000 description 1
- ADODRSVGNHNKAT-UHFFFAOYSA-N 2-Chlorophenylhydrazine hydrochloride Chemical compound Cl.NNC1=CC=CC=C1Cl ADODRSVGNHNKAT-UHFFFAOYSA-N 0.000 description 1
- UTWMSGSDWZDPOM-UHFFFAOYSA-N 2-methyl-3-phenylcyclobutan-1-one Chemical compound C1C(=O)C(C)C1C1=CC=CC=C1 UTWMSGSDWZDPOM-UHFFFAOYSA-N 0.000 description 1
- DGOAXBPOVUPPEB-UHFFFAOYSA-N 3-(difluoromethyl)-N-methoxy-1-methyl-N-[1-(2,4,6-trichlorophenyl)propan-2-yl]pyrazole-4-carboxamide Chemical compound C=1N(C)N=C(C(F)F)C=1C(=O)N(OC)C(C)CC1=C(Cl)C=C(Cl)C=C1Cl DGOAXBPOVUPPEB-UHFFFAOYSA-N 0.000 description 1
- UXDLLFIRCVPPQP-UHFFFAOYSA-N 4-hydrazinylbenzonitrile;hydrochloride Chemical compound [Cl-].[NH3+]NC1=CC=C(C#N)C=C1 UXDLLFIRCVPPQP-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 241000123650 Botrytis cinerea Species 0.000 description 1
- 241000723418 Carya Species 0.000 description 1
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 1
- 208000035240 Disease Resistance Diseases 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 239000001293 FEMA 3089 Substances 0.000 description 1
- 241000223218 Fusarium Species 0.000 description 1
- 241000238631 Hexapoda Species 0.000 description 1
- 241000218195 Lauraceae Species 0.000 description 1
- 208000031888 Mycoses Diseases 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 241000233614 Phytophthora Species 0.000 description 1
- 241000233622 Phytophthora infestans Species 0.000 description 1
- 241000221662 Sclerotinia Species 0.000 description 1
- 241000221696 Sclerotinia sclerotiorum Species 0.000 description 1
- 241000779819 Syncarpia glomulifera Species 0.000 description 1
- OPIOKSFIERNABH-UHFFFAOYSA-N [3,5-bis(trifluoromethyl)anilino]azanium;chloride Chemical compound Cl.NNC1=CC(C(F)(F)F)=CC(C(F)(F)F)=C1 OPIOKSFIERNABH-UHFFFAOYSA-N 0.000 description 1
- KQXZVSQCMVKMBK-UHFFFAOYSA-N [4-(trifluoromethoxy)phenyl]hydrazine;hydrochloride Chemical compound Cl.NNC1=CC=C(OC(F)(F)F)C=C1 KQXZVSQCMVKMBK-UHFFFAOYSA-N 0.000 description 1
- WCAGNYIHAYOPSE-UHFFFAOYSA-N [4-(trifluoromethyl)phenyl]hydrazine;hydrochloride Chemical compound [Cl-].[NH3+]NC1=CC=C(C(F)(F)F)C=C1 WCAGNYIHAYOPSE-UHFFFAOYSA-N 0.000 description 1
- 230000009418 agronomic effect Effects 0.000 description 1
- ZWWXDCOPVYATOQ-UHFFFAOYSA-N amino-(4-nitrophenyl)azanium;chloride Chemical compound [Cl-].N[NH2+]C1=CC=C([N+]([O-])=O)C=C1 ZWWXDCOPVYATOQ-UHFFFAOYSA-N 0.000 description 1
- 239000003429 antifungal agent Substances 0.000 description 1
- 229940121375 antifungal agent Drugs 0.000 description 1
- 244000000005 bacterial plant pathogen Species 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- LMIZORQOLSLQRY-UHFFFAOYSA-N benzene;naphthalene Chemical group C1=CC=CC=C1.C1=CC=CC2=CC=CC=C21 LMIZORQOLSLQRY-UHFFFAOYSA-N 0.000 description 1
- 150000001604 bicyclic monoterpene derivatives Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229940025250 camphora Drugs 0.000 description 1
- 239000010238 camphora Substances 0.000 description 1
- 229960001701 chloroform Drugs 0.000 description 1
- 239000002361 compost Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229940063123 diflucan Drugs 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- RFHAOTPXVQNOHP-UHFFFAOYSA-N fluconazole Chemical compound C1=NC=NN1CC(C=1C(=CC(F)=CC=1)F)(O)CN1C=NC=N1 RFHAOTPXVQNOHP-UHFFFAOYSA-N 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 244000053095 fungal pathogen Species 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000003306 harvesting Methods 0.000 description 1
- 229940042795 hydrazides for tuberculosis treatment Drugs 0.000 description 1
- ADTJGIMHXSBSPS-UHFFFAOYSA-N hydron;(2,4,6-trichlorophenyl)hydrazine;chloride Chemical compound Cl.NNC1=C(Cl)C=C(Cl)C=C1Cl ADTJGIMHXSBSPS-UHFFFAOYSA-N 0.000 description 1
- 238000000338 in vitro Methods 0.000 description 1
- 238000000099 in vitro assay Methods 0.000 description 1
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- 239000010410 layer Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000618 nitrogen fertilizer Substances 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000001739 pinus spp. Substances 0.000 description 1
- 239000011505 plaster Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000001846 repelling effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229940098465 tincture Drugs 0.000 description 1
- 229940036248 turpentine Drugs 0.000 description 1
- 230000017260 vegetative to reproductive phase transition of meristem Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C311/00—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
- C07C311/48—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups having nitrogen atoms of sulfonamide groups further bound to another hetero atom
- C07C311/49—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups having nitrogen atoms of sulfonamide groups further bound to another hetero atom to nitrogen atoms
-
- 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
- A01N41/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom
- A01N41/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom containing a sulfur-to-oxygen double bond
- A01N41/04—Sulfonic acids; Derivatives thereof
- A01N41/06—Sulfonic acid amides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/36—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of amides of sulfonic acids
- C07C303/38—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of amides of sulfonic acids by reaction of ammonia or amines with sulfonic acids, or with esters, anhydrides, or halides thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/72—Nitrogen atoms
- C07D213/76—Nitrogen atoms to which a second hetero atom is attached
- C07D213/77—Hydrazine radicals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2602/00—Systems containing two condensed rings
- C07C2602/36—Systems containing two condensed rings the rings having more than two atoms in common
- C07C2602/42—Systems containing two condensed rings the rings having more than two atoms in common the bicyclo ring system containing seven carbon atoms
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
The invention discloses a preparation method of camphor sulfonyl hydrazide compounds, products and application thereof, wherein the structural formula of the camphor sulfonyl hydrazide compounds is as follows:
the camphor sulfonyl hydrazide compound is applied to preventing and treating plant fungi in agriculture or forestry, and the activity result shows that: the compound provided by the invention has better control effects on wheat scab, phytophthora capsici and hickory nut dry rot.
Description
Technical Field
The invention belongs to the technical field of pesticide synthesis, and particularly relates to a preparation method of camphor sulfonyl hydrazine compounds, products and application thereof.
Background
Wheat scab is a major disease that compromises wheat growth. Wheat scab can cause seedling withering, ear rot, stem rot, stalk rot and ear rot, and the seedling can be damaged from seedling to ear emergence and needs to be prevented and treated in time.
The wheat scab control method comprises the following steps:
(1) selecting disease-resistant varieties: at present, although immune varieties are not found, some disease-resistant varieties with good agronomic characters exist, such as Sumai No. 3 and Sumai No. 2. Spring wheat includes Dingfeng No. 3 and Ningchun No. 24. Each place can be selected according to the local conditions.
(2) Agricultural control: reasonable irrigation and drainage, and ditches are required to be dug in the wetland for drainage. Deep ploughing and stubble cleaning are needed after harvesting, and the bacteria source is reduced. Timely seeding is carried out, and rain in the flowering period is avoided. The compost made by retting enzyme bacteria is advocated, a formula fertilization technology is adopted, and when fertilization is performed, nitrogen fertilizer is forbidden to be applied partially, so that the disease resistance of plants is improved.
On the other hand, in recent years, researches on terpenoids have attracted much attention in the medical or agricultural fields, and camphor, an important resource of forest products, is a non-woody forest product with a bicyclic monoterpene structure, naturally exists in Lauraceae plants, is a renewable natural dominant biomass resource in China, and has an IUPAC name of 1,7, 7-trimethylbicyclo [2.2.1 ] being a 1,7, 7-trimethylbicyclo]Heptane-2-one of formula C10H16And O. It is white or transparent waxy solid at room temperature, and can be used for repelling insects. The camphor is extracted from camphor tree trunks, and the camphor trees with the older ages are rich in camphor in a larger proportion. The refining method comprises cutting trunk into small pieces, distilling with water, heating oleum Camphora, rising with water vapor, and cooling in a pottery jar placed above. The traditional Chinese medicine preparation mainly utilizes the effects of cooling, fragrance, dispersion and pain relief. It is often added in the form of rubber ointment, tincture, plaster, oil and ointment. Therefore, the camphor is widely applied to the fields of medical intermediates, environment-friendly mothproofing agents, spices, incense, industrial raw materials and the like。
The camphor from natural sources can not meet the expanding market demand of camphor due to the reasons of resource shortage, protection and the like, so the synthetic camphor produced by taking turpentine as raw material can be produced at the same time. Because the turpentine oil is rich in resources, the synthetic camphor and the natural camphor have no essential difference in the aspects of chemical properties, application performance and the like, and the synthetic camphor can completely replace the natural camphor for use.
The preparation method of the camphor sulfonyl hydrazide compound and the application in sterilization are not reported.
Disclosure of Invention
This section is for the purpose of summarizing some aspects of embodiments of the invention and to briefly introduce some preferred embodiments. In this section, as well as in the abstract and the title of the invention of this application, simplifications or omissions may be made to avoid obscuring the purpose of the section, the abstract and the title, and such simplifications or omissions are not intended to limit the scope of the invention.
The present invention has been made keeping in mind the above and/or other problems occurring in the prior art.
Therefore, the object of the present invention is to overcome the disadvantages of the prior art and to provide camphorsulfonylhydrazide compounds.
In order to solve the technical problems, the invention provides the following technical scheme: the camphor sulfonyl hydrazide compound has the structural formula shown as follows:
wherein,
it is still another object of the present invention to provide a method for preparing camphorsulfonylhydrazide compounds, which overcomes the disadvantages of the prior art.
In order to solve the technical problems, the invention provides the following technical scheme: the preparation method of the camphor sulfonyl hydrazine compound comprises the steps of reacting L-10-camphor sulfonic acid with thionyl chloride to synthesize an L-10-camphor sulfonyl chloride intermediate;
reacting the L-10-camphorsulfonyl chloride intermediate with substituted phenylhydrazine hydrochloride, triethylamine and 4-dimethylamino pyridine to synthesize camphorsulfonyl hydrazide compounds I-1 to I-18;
the L-10-camphorsulfonyl chloride intermediate reacts with 1-naphthylhydrazine hydrochloride, triethylamine and 4-dimethylamino pyridine to synthesize the camphorsulfonyl hydrazide compound I-19.
As a preferable embodiment of the preparation method of the camphor sulfonyl hydrazide compound, the preparation method comprises the following steps: an intermediate of L-10-camphorsulfonyl chloride, a process for its preparation, comprising,
adding 3.0mmol of L-10-camphorsulfonic acid and 3.3mmol of thionyl chloride into a single-mouth bottle, heating to reflux temperature, reacting for 5 hours, cooling, concentrating and removing most of solvent and HCl to obtain white solid L-10-camphorsulfonyl chloride.
As a preferable embodiment of the preparation method of the camphor sulfonyl hydrazide compound, the preparation method comprises the following steps: the feeding molar ratio of the intermediate L-10-camphorsulfonyl chloride to the substituted phenylhydrazine hydrochloride is 1.1: 1.
As a preferable embodiment of the preparation method of the camphor sulfonyl hydrazide compound, the preparation method comprises the following steps: the feeding molar ratio of the substituted phenylhydrazine hydrochloride to the triethylamine is 1: 1.1.
As a preferable embodiment of the preparation method of the camphor sulfonyl hydrazide compound, the preparation method comprises the following steps: the molar ratio of the L-10-camphorsulfonyl chloride intermediate to 4-dimethylaminopyridine was 1.1: 0.1.
As a preferable embodiment of the preparation method of the camphor sulfonyl hydrazide compound, the preparation method comprises the following steps: synthesizing camphor sulfonyl hydrazide compounds I-1-I-18, wherein the synthesis reaction temperature is 25 ℃, and the reaction time is 5-10 h; the camphor sulfonyl hydrazine compound I-19 is synthesized by reaction, the reaction temperature is 25 ℃, and the reaction time is 5-10 h.
As a preferable embodiment of the preparation method of the camphor sulfonyl hydrazide compound, the preparation method comprises the following steps: the feeding molar ratio of the intermediate L-10-camphorsulfonyl chloride to the 1-naphthylhydrazine hydrochloride is 1.1: 1.
The invention also aims to overcome the defects in the prior art and provide the application of the camphor sulfonyl hydrazine compounds in preventing and controlling plant fungi in agriculture or forestry, wherein the plant fungi comprise wheat scab, phytophthora capsici and hickory nut stem rot.
The invention has the beneficial effects that:
(1) the camphor sulfonyl hydrazide compound has a novel molecular structure, and is a novel compound; the chemical structure is characterized in that the chemical structure is clear, the structural formula contains sulfonyl hydrazide, wherein a substituted benzene (naphthalene) group is connected with camphorsulfonic acid through sulfonyl hydrazide bonds; the preparation method of the compound is simple and convenient, the raw materials are easy to obtain, the reaction conditions are easy to control, and particularly in the step of synthesizing the camphor sulfonyl hydrazine compound, the product can be obtained through column chromatography.
(2) The compound of the invention is a medicament for preventing and treating plant fungi in the agricultural or forestry field, and the medicament has better prevention and treatment effects on wheat scab, phytophthora capsici leonian and hickory nut stem rot.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without inventive exercise. Wherein:
FIG. 1 is a schematic diagram of preparation methods of camphorsulfonyl hydrazide compounds I-1 to I-18 in the embodiment of the invention.
FIG. 2 is a schematic diagram showing a process for producing a camphorsulfonyl hydrazide compound I-19 in an example of the present invention.
FIG. 3 is a schematic diagram of the in vitro assay (plate) of Compound I-11 against Gibberella zeae in the present example (from left to right concentrations of 0.781mg/L,0.195mg/L,0.049mg/L,0.012mg/L and 0.003mg/L, respectively).
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention more comprehensible, specific embodiments thereof are described in detail below with reference to examples of the specification.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, however, the present invention may be practiced otherwise than as specifically described herein, and it will be appreciated by those skilled in the art that the present invention may be practiced without departing from the spirit and scope of the present invention and that the present invention is not limited by the specific embodiments disclosed below.
Furthermore, reference herein to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one implementation of the invention. The appearances of the phrase "in one embodiment" in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments.
Dissolving substituted phenylhydrazine hydrochloride (1.0mmol), 4-dimethylaminopyridine (0.1mmol) and triethylamine (1.1mmol) in anhydrous dichloromethane, cooling to 0 ℃, adding L-10-camphorsulfonyl chloride (1.1mol) in batches, raising the temperature to 25 ℃, and reacting for 5-10 h.
The TLC monitored the starting material reaction was complete, the organic layer was washed 3 times with water (8mL x 3), 3 times with saturated brine (8mL x 3), dried, filtered with suction, concentrated to remove dichloromethane, and the crude product was chromatographed (CH2Cl2: MeOH ═ 20:1) to give the target compounds I-1 to I-18. The preparation method of the camphor sulfonyl hydrazide compounds I-1 to I-18 is shown in figure 1.
In the invention, L-10-camphorsulfonic acid, 4-dimethylamino pyridine, triethylamine and substituted phenylhydrazine hydrochloride are all purchased from Shanghai Biao science and technology Limited; thionyl chloride was purchased from Tianjin polishing chemical plant; other raw materials are all common commercial products.
Example 1
Dissolving 2-chlorophenylhydrazine hydrochloride (1.0mmol), 4-dimethylaminopyridine (0.1mmol) and triethylamine (1.1mmol) in anhydrous dichloromethane, cooling to 0 deg.C, adding L-10-camphorsulfonyl chloride (1.1mol) in batches, and heating to room temperatureReacting at 25 deg.C for 5h, monitoring by TLC that the starting material has reacted completely, washing the organic layer with water 3 times (8 mL. times.3), washing with saturated saline 3 times (8 mL. times.3), drying, suction filtering, concentrating to remove dichloromethane, and subjecting the crude product to column Chromatography (CH)2Cl2MeOH ═ 20:1) to give the title compound I-1, white solid, m.p.150-151 ℃, yield: 60 percent.1H NMR(600MHz,CDCl3)δ7.38(dd,J＝8.2,1.3Hz,1H),7.25(d,J＝1.2Hz,1H),7.21(t,J＝8.4Hz,2H),6.85–6.82(m,1H),6.45(s,1H),3.79(d,J＝15.5Hz,1H),2.90(d,J＝15.5Hz,1H),2.49–2.44(m,1H),2.35–2.30(m,1H),2.18(t,J＝4.5Hz,1H),2.10–2.04(m,1H),1.99(J＝18.8Hz,1H),1.89–1.84(m,1H),1.52–1.47(m,1H),1.03(s,3H),0.94(s,3H).13C NMR(150MHz,CDCl3)δ218.84,143.07,129.08,127.88,121.35,118.57,115.14,59.06,49.46,46.65,43.07,42.68,27.13,26.12,19.85,19.35.
Example 2
Dissolving 4-cyanophenylhydrazine hydrochloride (1.0mmol), 4-dimethylaminopyridine (0.1mmol) and triethylamine (1.1mmol) in anhydrous dichloromethane, cooling to 0 ℃, adding L-10-camphorsulfonyl chloride (1.1mol) in batches, raising the temperature to 25 ℃, reacting for 5.5h, monitoring the completion of the reaction of the raw materials by TLC, washing an organic layer with water for 3 times (8mL x 3), washing with saturated saline water for 3 times (8mL x 3), drying, performing suction filtration, concentrating to remove dichloromethane, and performing column chromatography on a crude product (CH)2Cl2MeOH ═ 20:1) gave the title compound I-2, a brown solid, m.p.97-99.5 ℃ in 65% yield.1H NMR(600MHz,CDCl3)δ7.52(d,J＝8.2Hz,2H),7.06(d,J＝8.4Hz,2H),6.50(s,1H),3.68(d,J＝15.4Hz,1H),2.90(d,J＝15.4Hz,1H),2.48–2.44(m,1H),2.36–2.31(m,1H),2.20(t,J＝4.4Hz,1H),2.11–2.06(m,1H),2.00(d,J＝18.9Hz,1H),1.84–1.80(m,2H),1.53–1.49(m,1H),1.04(s,3H),0.93(s,3H).13C NMR(150MHz,CDCl3)δ219.30,150.67,133.59,119.57,113.36,103.28,59.03,49.57,46.89,43.06,42.59,27.07,25.92,19.85,19.29.
Example 3
Dissolving 4-trifluoromethylphenylhydrazine hydrochloride (1.0mmol), 4-dimethylaminopyridine (0.1mmol) and triethylamine (1.1mmol) in anhydrous dichloromethane, cooling to 0 ℃, adding L-10-camphorsulfonyl chloride (1.1mol) in batches, raising the temperature to 25 ℃, reacting for 6h, monitoring the completion of the reaction of the raw materials by TLC, washing an organic layer with water for 3 times (8mL x 3), washing with saturated saline solution for 3 times (8mL x 3), drying, performing suction filtration, concentrating to remove dichloromethane, and performing column chromatography on a crude product (CH)2Cl2MeOH ═ 20:1) gave the title compound I-3, a pale yellow solid, m.p.143-144 ℃, yield 67%.1H NMR(600MHz,CDCl3)δ7.49(d,J＝8.5Hz,2H),7.09(d,J＝8.5Hz,2H),6.90(s,1H),6.44(s,1H),3.70(d,J＝15.5Hz,1H),2.90(d,J＝15.5Hz,1H),2.51–2.41(m,1H),2.37–2.29(m,1H),2.19(t,J＝4.5Hz,1H),2.11–2.05(m,1H),1.99(d,J＝18.8Hz,1H),1.86–1.81(m,1H),1.52–1.48(m,1H),1.03(s,3H),0.93(s,3H).13C NMR(150MHz,CDCl3)δ218.94,149.85(d,J＝5.3Hz),126.47(t,J＝4.8Hz),124.49(q,J＝269.7Hz),122.85(q,J＝31.8Hz),121.64,113.09,59.01,49.42,46.81,43.02,42.60,27.04,25.96,19.79,19.29.
Example 4
Dissolving 4-nitrophenylhydrazine hydrochloride (1.0mmol), 4-dimethylaminopyridine (0.1mmol) and triethylamine (1.1mmol) in anhydrous dichloromethane, cooling to 0 ℃, adding L-10-camphorsulfonyl chloride (1.1mol) in batches, raising the temperature to 25 ℃, reacting for 8h, monitoring the completion of the reaction of raw materials by TLC, washing an organic layer with water for 3 times (8mL x 3), washing with saturated saline solution for 3 times (8mL x 3), drying, performing suction filtration, concentrating to remove dichloromethane, and performing column chromatography on a crude product (CH)2Cl2MeOH ═ 20:1) gave the title compound I-4, a pale yellow solid, m.p.140.7-141 ℃ in 30.1% yield.1H NMR(600MHz,CDCl3)δ8.13(d,J＝9.2Hz,2H),7.55–7.29(m,1H),7.05(d,J＝9.2Hz,2H),6.62(s,1H),3.68(d,J＝15.5Hz,1H),2.92(d,J＝15.5Hz,1H),2.48–2.44(m,1H),2.36–2.31(m,1H),2.20(t,J＝4.5Hz,1H),2.11–2.05(m,1H),2.00(d,J＝18.9Hz,1H),1.84–1.79(m,1H),1.53–1.48(m,1H),1.03(s,3H),0.93(s,3H).13C NMR(150MHz,CDCl3)δ219.53,152.50,141.13,125.79,112.39,59.01,49.63,46.84,43.04,42.53,27.04,25.82,19.81,19.26.
Example 5
Dissolving 4-chlorophenylhydrazine hydrochloride (1.0mmol), 4-dimethylaminopyridine (0.1mmol) and triethylamine (1.1mmol) in anhydrous dichloromethane, cooling to 0 ℃, adding L-10-camphorsulfonyl chloride (1.1mol) in batches, raising the temperature to 25 ℃, reacting for 9h, monitoring the reaction completion of raw materials by TLC, washing an organic layer with water for 3 times (8mL x 3), washing with saturated saline solution for 3 times (8mL x 3), drying, performing suction filtration, concentrating to remove dichloromethane, and performing column chromatography on a crude product (CH)2Cl2MeOH ═ 20:1) gave the title compound I-5 as a pale yellow solid, m.p.131-133 ℃, yield 33%.1H NMR(600MHz,CDCl3)δ7.21(d,J＝8.8Hz,2H),6.98(d,J＝8.8Hz,2H),6.40(s,1H),3.70(d,J＝15.5Hz,1H),2.88(d,J＝15.5Hz,1H),2.46–2.42(m,1H),2.34–2.29(m,1H),2.18(t,J＝4.4Hz,1H),2.10–2.04(m,1H),1.98(d,J＝18.8Hz,1H),1.87–1.83(m,1H),1.67(s,1H),1.51–1.47(m,1H),1.03(s,3H),0.92(s,3H).13C NMR(150MHz,CDCl3)δ218.66,145.67,129.01,125.95,115.17,58.99,49.37,46.90,43.02,42.60,27.05,26.03,19.85,19.33.
Example 6
Dissolving 3-chlorophenylhydrazine hydrochloride (1.0mmol), 4-dimethylaminopyridine (0.1mmol) and triethylamine (1.1mmol) in anhydrous dichloromethane, cooling to 0 ℃, adding L-10-camphorsulfonyl chloride (1.1mol) in batches, raising the temperature to 25 ℃, reacting for 8h, monitoring by TLC that the raw materials are completely reacted, washing the organic layer with water for 3 times (8ml x 3), and using saturated salt solutionWashing 3 times (8mL of 3), drying, filtering, concentrating to remove dichloromethane, and purifying the crude product by column Chromatography (CH)2Cl2MeOH ═ 20:1) gave the title compound I-6, a pale yellow solid, m.p.136.5-139.5 ℃ in 79.2% yield.1H NMR(600MHz,CDCl3)δ7.16(t,J＝8.0Hz,1H),7.06(t,J＝2.1Hz,1H),6.91–6.87(m,2H),6.43(s,1H),3.69(d,J＝15.5Hz,1H),2.89(d,J＝15.5Hz,1H),2.46–2.41(m,1H),2.34–2.28(m,1H),2.18(t,J＝4.5Hz,1H),2.10–2.04(m,1H),1.98(d,J＝18.8Hz,1H),1.87–1.82(m,1H),1.51–1.47(m,1H),1.02(s,3H),0.92(s,3H).13C NMR(150MHz,CDCl3)δ218.74,148.29,134.95,130.16,121.16,113.91,111.96,59.00,49.39,46.89,43.01,42.60,27.05,26.01,19.81,19.30.
Example 7
Dissolving 4-fluorophenylhydrazine hydrochloride (1.0mmol), 4-dimethylaminopyridine (0.1mmol) and triethylamine (1.1mmol) in anhydrous dichloromethane, cooling to 0 ℃, adding L-10-camphorsulfonyl chloride (1.1mol) in batches, raising the temperature to 25 ℃, reacting for 10h, monitoring the reaction completion of raw materials by TLC, washing an organic layer with water for 3 times (8mL x 3), washing with saturated saline water for 3 times (8mL x 3), drying, performing suction filtration, concentrating to remove dichloromethane, and performing column Chromatography (CH) on a crude product2Cl2MeOH ═ 20:1) to give the title compound I-7, a pale yellow solid, m.p.91-93 ℃ yield 51%.1HNMR(600MHz,CDCl3)δ7.07–6.83(m,4H),6.43(s,1H),3.70(d,J＝15.4Hz,1H),2.87(d,J＝15.5Hz,1H),2.46–2.41(m,1H),2.33–2.28(m,1H),2.18(t,J＝4.5Hz,1H),2.10–2.04(m,1H),1.97(d,J＝18.8Hz,1H),1.88–1.84(m,1H),1.51–1.47(m,1H),1.02(s,3H),0.92(s,3H).13C NMR(150MHz,CDCl3)δ218.58,158.03(d,J＝237.5Hz),143.13(d,J＝2.3Hz),115.66(d,J＝22.6Hz),115.41(d,J＝7.8Hz),115.41(d,J＝7.8Hz),59.04,49.37,46.85,43.05,42.64,27.08,26.13,19.85,19.35.
Example 8
Dissolving 2,4, 6-trichlorophenylhydrazine hydrochloride (1.0mmol), 4-dimethylaminopyridine (0.1mmol) and triethylamine (1.1mmol) in anhydrous dichloromethane, cooling to 0 ℃, adding L-10-camphorsulfonyl chloride (1.1mol) in batches, raising the temperature to 25 ℃, reacting for 9.5h, monitoring the completion of the reaction of the raw materials by TLC, washing an organic layer with water for 3 times (8mL x 3), washing with saturated saline for 3 times (8mL 3), drying, performing suction filtration, concentrating to remove dichloromethane, performing column chromatography on a crude product (CH)2Cl2MeOH, 20:1) gave the title compound, I-8, as a white solid, m.p. 128.9-129.5 ℃ with a yield of 90.5%.1H NMR(600MHz,CDCl3)δ7.30(s,2H),7.19(s,1H),6.67(s,1H),3.62(d,J＝15.3Hz,1H),2.83(d,J＝15.4Hz,1H),2.45–2.33(m,2H),2.16(t,J＝4.5Hz,1H),2.08–2.03(m,1H),1.98(d,J＝18.7Hz,1H),1.82–1.77(m,1H),1.50–1.46(m,1H),1.01(s,3H),0.86(s,3H).13C NMR(150MHz,CDCl3)δ217.13,138.93,128.99,128.73,127.55,58.58,48.87,48.03,42.73,42.55,26.97,25.00,19.66,19.38.
Example 9
Dissolving 4-trifluoromethoxy phenylhydrazine hydrochloride (1.0mmol), 4-dimethylamino pyridine (0.1mmol) and triethylamine (1.1mmol) in anhydrous dichloromethane, cooling to 0 ℃, adding L-10-camphorsulfonyl chloride (1.1mol) in batches, raising the temperature to 25 ℃, reacting for 6.5h, monitoring the completion of the reaction of the raw materials by TLC, washing an organic layer with water for 3 times (8mL x 3), washing with saturated saline water for 3 times (8mL x 3), drying, performing suction filtration, concentrating to remove dichloromethane, and performing column chromatography on a crude product (CH)2Cl2MeOH ═ 20:1) to give the title compound I-9, a beige solid, in 30% yield at m.p.95-97 ℃.1H NMR(600MHz,CDCl3)δ7.11(d,J＝8.7Hz,2H),7.04(d,J＝9.0Hz,2H),6.45(s,1H),3.71(d,J＝15.5Hz,1H),2.88(d,J＝15.5Hz,1H),2.46–2.42(m,1H),2.33–2.29(m,1H),2.18(t,J＝4.4Hz,1H),2.10–2.06(m,1H),1.98(d,J＝18.8Hz,1H),1.88–1.83(m,1H),1.51–1.47(m,1H),1.02(s,3H),0.92(s,3H).13C NMR(150MHz,CDCl3)δ218.91,145.73,143.21(d,J＝1.5Hz),122.22,118.8(q,J＝254.6Hz),114.57,59.01,49.45,46.68,43.03,42.57,27.05,26.04,19.81,19.29.
Example 10
Dissolving 4-bromophenylhydrazine hydrochloride (1.0mmol), 4-dimethylaminopyridine (0.1mmol) and triethylamine (1.1mmol) in anhydrous dichloromethane, cooling to 0 ℃, adding L-10-camphorsulfonyl chloride (1.1mol) in batches, raising the temperature to 25 ℃, reacting for 7.5h, monitoring the completion of the reaction of the raw materials by TLC, washing an organic layer with water for 3 times (8mL x 3), washing with saturated saline solution for 3 times (8mL x 3), drying, performing suction filtration, concentrating to remove dichloromethane, and performing column chromatography on a crude product (CH)2Cl2MeOH ═ 20:1) gave the title compound I-10 as a beige solid, m.p.109-111.5 ℃ in 20.5% yield.1H NMR(600MHz,CDCl3)δ7.34(d,J＝8.8Hz,2H),6.93(d,J＝8.8Hz,2H),6.40(s,1H),3.70(d,J＝15.5Hz,1H),2.88(d,J＝15.5Hz,1H),2.46–2.42(m,1H),2.34–2.29(m,1H),2.18(t,J＝4.5Hz,1H),2.10–2.05(m,1H),1.98(d,J＝18.8Hz,1H),1.87–1.82(m,1H),1.51–1.47(m,1H),1.03(s,3H),0.92(s,3H).13C NMR(150MHz,CDCl3)δ218.65,146.20,131.91,115.55,113.20,58.99,49.37,46.79,43.01,42.61,27.05,26.00,19.82,19.33.
Example 11
Dissolving 2-chloro-4-fluorophenylhydrazine hydrochloride (1.0mmol), 4-dimethylaminopyridine (0.1mmol) and triethylamine (1.1mmol) in anhydrous dichloromethane, cooling to 0 ℃, adding L-10-camphorsulfonyl chloride (1.1mol) in batches, raising the temperature to 25 ℃ for reaction for 5.5h, monitoring the completion of the reaction of the raw materials by TLC, washing the organic layer with water for 3 times (8mL x 3), washing the organic layer with saturated saline water for 3 times (8mL x 3), drying, suction filtering, concentrating to remove dichloromethane, and performing column chromatography on the crude product (CH)2Cl2MeOH 20:1) to obtain the target compound I-11, beige solidM.p.133.1-135 deg.C, yield 79%.1H NMR(600MHz,CDCl3)δ7.35(dd,J＝9.1,5.3Hz,1H),7.11(s,1H),7.03(dd,J＝8.1,2.8Hz,1H),6.97–6.94(m,1H),6.45(s,1H),3.79(d,J＝15.5Hz,1H),2.89(d,J＝15.5Hz,1H),2.49–2.45(m,1H),2.34–2.29(m,1H),2.19(t,J＝4.5Hz,1H),2.10–2.05(m,1H),1.99(d,J＝18.8Hz,1H),1.88–1.84(m,1H),1.52–1.48(m,1H),1.04(s,3H),0.94(s,3H).13C NMR(150MHz,CDCl3)δ219.13,156.76(d,J＝240.5Hz),139.70,118.58(d,J＝10.5Hz),116.16(d,J＝3.9Hz),116.05(d,J＝13.8Hz),114.76(d,J＝21.9Hz),59.02,49.5,46.41,43.05,42.59,27.08,26.06,19.80,19.29.
Example 12
Dissolving 3, 5-bis (trifluoromethyl) phenylhydrazine hydrochloride (1.0mmol), 4-dimethylamino pyridine (0.1mmol) and triethylamine (1.1mmol) in anhydrous dichloromethane, cooling to 0 deg.C, adding L-10-camphorsulfonyl chloride (1.1mol) in batches, heating to 25 deg.C, reacting for 6.5h, monitoring by TLC that the raw materials are completely reacted, washing the organic layer with water for 3 times (8mL x 3), washing with saturated saline solution for 3 times (8mL x 3), drying, suction filtering, concentrating to remove dichloromethane, and performing column chromatography on the crude product (CH)2Cl2MeOH 20:1) gave the title compound I-12 as a white solid, m.p.136.5-137.5 ℃, yield 29.0%.1H NMR(600MHz,CDCl3)δ7.45(s,2H),7.38(s,1H),7.18(s,1H),6.48(s,1H),3.71(d,J＝15.6Hz,1H),2.92(d,J＝15.6Hz,1H),2.49–2.45(m,1H),2.37–2.31(m,1H),2.22(t,J＝4.5Hz,1H),2.13–2.07(m,1H),2.01(d,J＝18.9Hz,1H),1.86–1.81(m,1H),1.54–1.50(m,1H),1.04(s,3H),0.95(s,3H).13C NMR(150MHz,CDCl3)δ219.62,148.32,132.4(q,J＝33.0Hz),123.3(q,J＝271.1Hz),120.53,114.17(q,J＝3.8Hz),113.24(d,J＝3.0Hz),59.05,49.65,46.70,43.04,42.54,27.01,25.96,19.75,19.20.
Example 13
Dissolving 2, 4-dichlorohydrazinium hydrochloride (1.0mmol), 4-dimethylaminopyridine (0.1mmol) and triethylamine (1.1mmol) in anhydrous dichloromethane, cooling to 0 ℃, adding L-10-camphorsulfonyl chloride (1.1mol) in batches, raising the temperature to 25 ℃, reacting for 6h, monitoring the completion of the reaction of the raw materials by TLC, washing an organic layer with water for 3 times (8mL x 3), washing with saturated saline water for 3 times (8mL x 3), drying, performing suction filtration, concentrating to remove dichloromethane, and performing column chromatography on a crude product (CH)2Cl2MeOH ═ 20:1) gave the title compound I-13 as a beige solid, m.p.125-126.5 ℃ in 76.1% yield.1H NMR(600MHz,CDCl3)δ7.32(d,J＝8.8Hz,1H),7.25(s,2H),7.18(dd,J＝8.8,2.2Hz,1H),6.44(s,1H),3.77(d,J＝15.5Hz,1H),2.89(d,J＝15.5Hz,1H),2.49–2.45(m,1H),2.35–2.30(m,1H),2.19(t,J＝4.4Hz,1H),2.11–2.01(m,1H),1.99(d,J＝18.9Hz,1H),1.87–1.82(m,1H),1.52–1.48(m,1H),1.04(s,3H),0.94(s,3H).13C NMR(150MHz,CDCl3)δ219.14,141.96,128.61,127.94,125.42,118.78,115.94,77.00,59.03,49.52,46.54,43.05,42.62,27.09,26.04,19.81,19.29.
Example 14
Dissolving 4-iodophenylhydrazine hydrochloride (1.0mmol), 4-dimethylaminopyridine (0.1mmol) and triethylamine (1.1mmol) in anhydrous dichloromethane, cooling to 0 ℃, adding L-10-camphorsulfonyl chloride (1.1mol) in batches, raising the temperature to 25 ℃, reacting for 5 hours, monitoring the reaction completion of the raw materials by TLC, washing an organic layer with water for 3 times (8mL x 3), washing with saturated saline for 3 times (8mL x 3), drying, performing suction filtration, concentrating to remove dichloromethane, and performing column chromatography on a crude product (CH)2Cl2MeOH 20:1) gave the title compound I-14 as a pale yellow solid, m.p. 101-103 ℃.1H NMR(600MHz,CDCl3)δ7.52(d,J＝8.6Hz,2H),6.82(d,J＝8.7Hz,2H),6.38(s,1H),3.69(d,J＝15.4Hz,1H),2.87(d,J＝15.4Hz,1H),2.46–2.42(m,1H),2.34–2.29(m,1H),2.18(t,J＝4.4Hz,1H),2.09–2.07(m,1H),1.98(d,J＝18.8Hz,1H),1.86–1.82(m,1H),1.51–1.47m,1H),1.03(s,3H),0.92(s,3H).13C NMR(150MHz,CDCl3)δ218.73,146.84,137.83,115.98,83.04,59.02,49.41,46.86,43.04,42.62,27.08,26.05,19.85,19.33.
Example 15
Dissolving 2, 4-difluorophenylhydrazine hydrochloride (1.0mmol), 4-dimethylaminopyridine (0.1mmol) and triethylamine (1.1mmol) in anhydrous dichloromethane, cooling to 0 ℃, adding L-10-camphorsulfonyl chloride (1.1mol) in portions, raising the temperature to 25 ℃ for reaction for 5.5h, monitoring the completion of the reaction of the raw materials by TLC, washing the organic layer with water for 3 times (8 mL. x.3), washing with saturated saline for 3 times (8 mL. x.3), drying, suction filtering, concentrating to remove dichloromethane, and performing column chromatography on the crude product (CH)2Cl2MeOH ═ 20:1) gave the title compound I-15 as a yellow solid, m.p.103-105 ℃ in 65% yield.1H NMR(600MHz,CDCl3)δ7.36–7.32(m,1H),6.84–6.78(m,2H),6.45(s,1H),3.76(d,J＝15.5Hz,1H),2.89(d,J＝15.5Hz,1H),2.48–2.44(m,1H),2.33–2.27(m,1H),2.19(t,J＝4.5Hz,1H),2.10–2.06(m,1H),1.98(d,J＝18.8Hz,1H),1.90–1.85(m,1H),1.52–1.48(m,1H),1.03(s,3H),0.94(s,3H).13C NMR(150MHz,CDCl3)δ218.89,156.86(d,J＝239.4,10.7Hz),150.31(d,J＝241.5,12.0Hz),131.61(dd,J＝10.5,3.1Hz),116.94(dd,J＝8.9,3.3Hz),111.22(dd,J＝21.9,3.6Hz),103.54(d,J＝22.1Hz),103.36(d,J＝22.2Hz),103.28,59.06,49.45,46.58,43.03,42.64,27.07,26.18,19.84,19.31.
Example 16
Dissolving 2-pyridylhydrazine hydrochloride (1.0mmol), 4-dimethylaminopyridine (0.1mmol) and triethylamine (1.1mmol) in anhydrous dichloromethane, cooling to 0 ℃, adding L-10-camphorsulfonyl chloride (1.1mol) in batches, raising the temperature to 25 ℃, reacting for 6h, monitoring the completion of the reaction of the raw materials by TLC, washing an organic layer with water for 3 times (8mL x 3), washing with saturated saline solution for 3 times (8mL x 3), drying, filtering, concentrating, and performing concentrationDichloromethane is removed and the crude product is Chromatographed (CH)2Cl2MeOH ═ 20:1) gave the title compound I-16, a yellow solid, m.p.163-165 ℃ in 69% yield.1H NMR(600MHz,CDCl3)δ8.11(d,J＝5.9Hz,1H),7.63–7.56(m,1H),7.49(s,1H),7.10(d,J＝8.4Hz,1H),6.81(dd,J＝6.8,4.8Hz,1H),3.80(d,J＝15.5Hz,1H),2.91(d,J＝15.5Hz,1H),2.43–2.39(m,1H),2.26–2.22(m,1H),2.14(t,J＝4.5Hz,1H),2.07–2.01(m,1H),1.97–1.93(m,2H),1.49–1.44(m,1H),1.01(s,3H),0.86(s,3H).13C NMR(150MHz,CDCl3)δ217.72,158.61,146.90,138.57,116.52,108.38,59.17,49.21,47.08,42.98,42.74,27.05,26.45,19.74,19.35.
Example 17
Dissolving 3-fluorophenylhydrazine hydrochloride (1.0mmol), 4-dimethylaminopyridine (0.1mmol) and triethylamine (1.1mmol) in anhydrous dichloromethane, cooling to 0 ℃, adding L-10-camphorsulfonyl chloride (1.1mol) in batches, raising the temperature to 25 ℃ for reacting for 6.5h, monitoring the complete reaction of the raw materials by TLC, washing an organic layer with water for 3 times (8mL x 3), washing an organic layer with saturated saline solution for 3 times (8mL x 3), drying, performing suction filtration, concentrating to remove dichloromethane, and performing column chromatography on a crude product (CH)2Cl2MeOH ═ 20:1) gave the title compound I-17 as a yellow solid, m.p.139-139.5 ℃ in 59% yield.1H NMR(600MHz,CDCl3)δ7.17(td,J＝8.1,6.4Hz,1H),6.84–6.73(m,2H),6.59(td,J＝8.4,2.3Hz,1H),6.49(s,1H),3.69(d,J＝15.4Hz,1H),2.89(d,J＝15.4Hz,1H),2.46–2.41(m,1H),2.33–2.28(m,1H),2.17(t,J＝4.5Hz,1H),2.09–2.03(m,1H),1.97(d,J＝18.8Hz,1H),1.86–1.81(m,1H),1.50–1.46(m,1H),1.02(s,3H),0.91(s,3H).13C NMR(150MHz,CDCl3)δ218.66,163.71(d,J＝243.0Hz),148.96(d,J＝10.2Hz),130.35(d,J＝9.6Hz),109.27(d,J＝2.6Hz),107.76(d,J＝21.4Hz),101.25(d,J＝26.0Hz),77.00,59.00,49.38,46.91,43.01,42.61,27.05,26.02,19.81,19.31.
Example 18
Dissolving 2-fluorophenylhydrazine hydrochloride (1.0mmol), 4-dimethylaminopyridine (0.1mmol) and triethylamine (1.1mmol) in anhydrous dichloromethane, cooling to 0 ℃, adding L-10-camphorsulfonyl chloride (1.1mol) in batches, raising the temperature to 25 ℃, reacting for 6.5h, monitoring the reaction completion of the raw materials by TLC, washing an organic layer with water for 3 times (8mL x 3), washing with saturated saline water for 3 times (8mL x 3), drying, performing suction filtration, concentrating to remove dichloromethane, and performing column chromatography on a crude product (CH)2Cl2MeOH ═ 20:1) gave the title compound I-18 as a yellow solid, m.p.137.9-138.5 ℃ in 60% yield.1H NMR(600MHz,CDCl3)δ7.37(td,J＝8.4,1.6Hz,1H),7.08(t,J＝7.8Hz,1H),7.02–6.99(m,1H),6.86–6.83(m,2H),6.44(s,1H),3.76(d,J＝15.5Hz,1H),2.90(d,J＝15.5Hz,1H),2.48–2.43(m,1H),2.34–2.29(m,1H),2.18(t,J＝4.5Hz,1H),2.10–2.05(m,1H),1.98(d,J＝18.8Hz,1H),1.90–1.85(m,1H),1.51–1.47(m,1H),1.03(s,3H),0.94(s,3H).13C NMR(150MHz,CDCl3)δ218.59,150.83(d,J＝238.4Hz),135.15(d,J＝10.0Hz),124.67(d,J＝3.5Hz),121.03(d,J＝7.0Hz),116.02(d,J＝2.1Hz),114.80(d,J＝17.9Hz),59.03,49.36,46.70,42.99,42.64,27.06,26.11,19.83,19.33.
Example 19
The method of the camphor sulfonyl hydrazide compound I-19 is schematically shown in figure 2, and the specific preparation process comprises the following steps:
1-naphthylhydrazine hydrochloride (1.0mmol), 4-dimethylaminopyridine (0.1mmol) and triethylamine (1.1mmol) are dissolved in anhydrous dichloromethane, the temperature is reduced to 0 ℃, L-10-camphorsulfonyl chloride (1.1mol) is added in batches, and the mixture is heated to 25 ℃ for reaction for 6 hours. The TLC monitored the starting material reaction was complete, the organic layer was washed 3 times with water (8mL x 3), 3 times with saturated brine (8mL x 3), dried, filtered with suction, concentrated to remove dichloromethane, and the crude product was chromatographed (CH2Cl2: MeOH ═ 20:1) to give the title compound I-19. brown solid, m.p.133.8-135.1 ℃ yield 65%.
1H NMR(600MHz,CDCl3)δ7.91(d,J＝8.8Hz,1H),7.84–7.82(m,1H),7.50–7.37(m,5H),6.33(s,1H),3.83(d,J＝15.5Hz,1H),2.93(d,J＝15.5Hz,1H),2.51–2.38(m,2H),2.19(t,J＝4.4Hz,1H),2.10–1.99(m,1H),2.01(d,J＝18.8Hz,1H),1.88–1.83(m,1H),1.52–1.48(m,1H),1.03(s,3H),0.93(s,3H).13C NMR(150MHz,CDCl3)δ218.74,141.75,134.06,128.60,126.24,125.86,125.40,122.66,121.19,119.81,108.61,58.97,49.34,46.98,43.03,42.57,27.05,25.75,19.78,19.33.
Example 20
Dissolving 2-chloro-4-fluorophenylhydrazine hydrochloride (1.0mmol), 4-dimethylaminopyridine (0.1mmol) and triethylamine (1.1mmol) in the solution, cooling to 0 ℃, adding L-10-camphorsulfonyl chloride (1.1mol) in batches, raising the temperature to 25 ℃ and reacting for 5.5 h. The reaction is post-treated to obtain the compound I-11, and the yield is counted.
The yield factors of three solvents for the hydrazidation reaction are discussed, wherein dichloromethane is used as the solvent, and the reaction yield is highest (79%); using trichloromethane as solvent, the yield is inferior; tetrahydrofuran is used as solvent, and the yield is lowest (50%). Therefore, methylene chloride is most preferably used as a solvent for the hydrazide reaction.
Example 21
Bactericidal activity (in vitro) test
The plant fungi used in the experiment are strains stored at 4 ℃ in a laboratory, such as botrytis cinerea, fusarium graminearum, potato late blight, phytophthora capsici, hickory nut stem rot, sclerotinia sclerotiorum, apple ring rot and rice sheath blight. The adopted culture medium is a potato agar glucose culture medium (PDA for short). The PDA culture medium formula comprises 200g of potato (peeled), 20g of glucose, 15g of agar and 1000mL of distilled water, and the preparation method comprises the following steps: cleaning and peeling potatoes, weighing 200g of potatoes, cutting the potatoes into small pieces, adding water, boiling the potatoes thoroughly (boiling for 20-30 minutes and being capable of being punctured by a glass rod), filtering the potatoes in a beaker by eight layers of gauze, adding 15-20 g of agar according to experimental requirements, adding 20g of glucose, stirring the mixture evenly, slightly cooling the mixture after the mixture is fully dissolved, supplementing water to 1000mL, sterilizing the mixture for 15 minutes at 121 ℃ after split charging, and cooling the mixture for later use.
The experimental method comprises the following steps: a growth rate method is used.
(1) Firstly, 8 plant fungi are cultured on a PDA flat plate at 25 ℃ for about 3-6 days for later use;
(2) heating PDA culture medium to melt, cooling to 45-50 deg.C, adding 250 μ L of 10g/L compound to be tested to obtain culture medium containing 50mg/L medicinal liquid, and respectively cooling in culture dish to obtain a positive control of diflucan hydroxylamine (pydiflumetofen);
(3) using a puncher to punch a circular fungus cake (with the diameter of 0.50cm) at the edge of each strain hypha (the growth condition is consistent as much as possible) cultured for 6d in a sterile operation, then using an inoculating needle to pick the disc to the center of a drug-containing flat plate, and then placing the culture dish in an incubator (28 ℃) for culture;
(4) observing and measuring the growth condition of hyphae at different time after treatment, measuring the diameter by adopting a cross method, processing data and calculating the inhibition rate;
(5) inhibition (%) × (control hypha diameter-treated hypha diameter)/(control hypha diameter-0.5) × 100;
(6) each treatment was repeated 3 times.
TABLE 1 test results of inhibitory Activity of Camphorsulfonyl hydrazides against eight agricultural pathogenic fungi
Note a three replicates per treatment were set up in the experiment and the data in the table are the average of the three replicates.
EC of part of the Compounds of Table 250Value of
The results of the bactericidal activity measurements of the experimental groups I-1 to I-19 and the control agent fluxapyroxad are shown in tables 1 and 2. As can be seen from the results in tables 1 and 2, at a concentration of 50mg/L, the compounds I-1 to I-19 showed bactericidal activities of different degrees on 8 plant fungi, and part of the compounds had better inhibitory activities on Phytophthora capsici, Gibberella zeae and Sclerotinia hickory; wherein the inhibition rate of the compound I-6, I-8 and I-13 to phytophthora capsici in the concentration of 50mg/L reaches 98 percent;
in addition, the inhibition rate of the compounds on the hickory nut dry rot is more than 90 percent, and is equivalent to that of positive control fluxapyroxad hydroxylamine; for wheat scab, the inhibition rate of individual compounds such as I-1, I-6, I-11, I-13, I-15 and I-17 on the wheat scab reaches 90%, which is equivalent to that of positive control fluxapyroxad.
As the target compound has better inhibitory activity to several plant pathogenic bacteria, the EC of the compound with higher inhibition rate of the general sieve is tested50The value is obtained. EC of a part of the Compounds50As shown in Table 2, it can be seen that the compounds I-1, I-11 and I-13 have EC against Gibberella cerealis50All values are less than 1.0mg/L, EC of Compound I-1150The value was 0.407mg/L, close to the positive control fluxapyroxad hydroxylamine (0.296 mg/L). In addition, part of the compounds have EC against Phytophthora capsici50Values were between 0.9-1.5mg/L, close to the positive control. The series of compounds have good inhibitory activity on several fungi and have the potential of developing antifungal agents.
The camphor compound containing the sulfonyl hydrazide group has obvious structural difference and distinct chemical structural characteristics, and has better effect on preventing and treating wheat scab, phytophthora capsici leonian and hickory nut dry rot. Can be used for preventing and treating fungal diseases of agricultural or forestry plants. The preparation method of the compound is simple and convenient, the yield is high, and the product property is stable.
It should be noted that the above-mentioned embodiments are only for illustrating the technical solutions of the present invention and not for limiting, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, which should be covered by the claims of the present invention.
Claims (10)
1. The camphor sulfonyl hydrazide compound is characterized in that: the structural formula of the camphor sulfonyl hydrazine compound is shown as follows:
2. the process for producing a camphorsulfonyl hydrazide compound as claimed in claim 1, wherein: comprises the steps of (a) preparing a substrate,
reacting the L-10-camphorsulfonic acid with thionyl chloride to synthesize an L-10-camphorsulfonyl chloride intermediate;
reacting the L-10-camphorsulfonyl chloride intermediate with substituted phenylhydrazine hydrochloride, triethylamine and 4-dimethylamino pyridine to synthesize camphorsulfonyl hydrazide compounds I-1 to I-18;
the L-10-camphorsulfonyl chloride intermediate reacts with 1-naphthylhydrazine hydrochloride, triethylamine and 4-dimethylamino pyridine to synthesize the camphorsulfonyl hydrazide compound I-19.
3. The process for producing a camphorsulfonyl hydrazide compound as claimed in claim 2, wherein: an intermediate of L-10-camphorsulfonyl chloride, a process for its preparation, comprising,
adding 3.0mmol of L-10-camphorsulfonic acid and 3.3mmol of thionyl chloride into a single-mouth bottle for dissolving, heating to the reflux temperature for reaction for 5 hours, cooling, concentrating and removing most of solvent and HCl to obtain white solid L-10-camphorsulfonyl chloride.
4. The process for producing a camphorsulfonyl hydrazide compound as claimed in claim 2, wherein: the feeding molar ratio of the intermediate L-10-camphorsulfonyl chloride to the substituted phenylhydrazine hydrochloride is 1.1: 1.
5. The process for producing a camphorsulfonyl hydrazide compound as claimed in claim 2, wherein: the feeding molar ratio of the substituted phenylhydrazine hydrochloride to the triethylamine is 1: 1.1.
6. The process for producing a camphorsulfonyl hydrazide compound as claimed in claim 2, wherein: the molar ratio of the L-10-camphorsulfonyl chloride intermediate to the 4-dimethylaminopyridine was 1.1: 0.1.
7. The process for the preparation of camphorsulfonyl hydrazines as claimed in claim 2 wherein: synthesizing camphor sulfonyl hydrazide compounds I-1-I-18, wherein the synthesis reaction temperature is 25 ℃, and the reaction time is 5-10 h; the camphor sulfonyl hydrazide compound I-19 is synthesized by reaction, the reaction temperature is 25 ℃, and the reaction time is 5-10 h.
8. The process for the preparation of camphorsulfonyl hydrazines as claimed in claim 2 wherein: the feeding molar ratio of the intermediate L-10-camphorsulfonyl chloride to the 1-naphthylhydrazine hydrochloride is 1.1: 1.
9. The use of camphorsulfonyl hydrazide compounds as claimed in claim 1 for controlling plant fungi in agriculture or forestry.
10. The use of claim 9, wherein: the plant fungi include Gibberella zeae, Phytophthora capsici and Carya cathayensis.
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| CN115197134A (en) * | 2022-07-14 | 2022-10-18 | 南京林业大学 | Preparation method and application of camphorsulfonate compounds |
| CN115197134B (en) * | 2022-07-14 | 2024-07-30 | 南京林业大学 | Preparation method and application of camphorsulfonate compounds |
| CN116813572A (en) * | 2023-05-31 | 2023-09-29 | 南京林业大学 | Preparation method of camphoric acid formylhydrazine compound, product and application thereof |
| CN116813572B (en) * | 2023-05-31 | 2024-03-12 | 南京林业大学 | Preparation method of camphoric acid formylhydrazine compound, product and application thereof |
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