CN101239973A - Substituted aminoquinazolinone (thione) derivative or salts thereof, intermediate compound therefor, pest-controlling agent and using method thereof - Google Patents
Substituted aminoquinazolinone (thione) derivative or salts thereof, intermediate compound therefor, pest-controlling agent and using method thereof Download PDFInfo
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Abstract
A pest control agent comprising substituted aminoquinazolinone (thione) derivatives or salts thereof represented by formula (I) as activity ingredients is disclosed, [wherein R is H, OH, formacyl, halogenated C<1-6>alkyl, hydroxyl C<1-6>alkyl, C<2-6>alkenyl, (substituted)aminoC<1-6>alkyl, (substituted)amino carbonyl, (substituted)phenylC<1-3>alkyl, (substituted)phenyl alkynylC<1-3>alkyl, 1,3-dioxolane-2-yl-C<1-3>alkyl, phthalic iminoC<1-6>alkyl and so on; R<1> is 5- or 6-member heterocycle including 1 to 3 heteroatoms selected from the group consisting of O, S and N; Y is O or S; Z is a group of formula -N=C(R<2>)- or formula -N(R<3>)-CH(R<2>)- (wherein R<2> and R<3> are hydrogen atoms, C<1-6>alkyl and so on); X is Br, I, OH, CN, C<1-6>alkyl, C<2-6>alkenyl, (substituted) amino carbonyl, (substituted)phenoxyl and so on; n is preferably an integer ranging from 0 to 4], and the substituted aminoquinazolinone derivatives or salts thereof has great insecticidal effect to Trialeurodes vaporariorum at a low dosage, nonetheless, general compounds including the similar chemical structure does not include the insecticidal effect.
Description
The aminoquinazolinone that the present invention relates to replace (thioketones) derivative or its salt, it prepares used intermediate and agent for controlling noxious insect pests and using method thereof.
Japanese unexamined publication JP-A-8-325239 discloses the amido quinazoline ketone derivatives as agent for controlling noxious insect pests.
Inventor of the present invention finds when conscientiously exploring new agent for controlling noxious insect pests, when low dosage, on the phenyl that belongs to the quinazolinone ring, have substituent The compounds of this invention and have identical with the disclosed embodiment compound of above-mentioned JP-A-8-325239 or better insecticidal effect.Particularly The compounds of this invention has gratifying insecticidal effect to the aleyrodid class that agriculture and horticulture relate to, and inventor of the present invention has thus finished the present invention.
The midbody compound (II) of preparation general formula (I) derivative of aminoquinazolinone (thioketones) derivative of the replacement of general formula (I) expression or its salt and general formula (II) expression is all undocumented new compound of any technical literature formerly.In addition, compare, when low dosage, contain aminoquinazolinone (thioketones) derivative of replacement of general formula (I) expression or its salt and various insects are all had outstanding insecticidal effect as the agent for controlling noxious insect pests of active ingredient with conventional agent for controlling noxious insect pests.
In order to develop the novel agent for controlling noxious insect pests with wideer insecticidal spectrum, inventor of the present invention has conscientiously studied aminoquinazolinone (thioketones) derivative.Last inventor of the present invention finds to have bromine atoms on the quinazoline ring, the iodine atom, and perfluoroalkyl, the new amido quinazoline ketone derivatives of perfluoro alkoxy etc. has very outstanding insecticidal effect as agent for controlling noxious insect pests.
The present invention relates to aminoquinazolinone (thioketones) derivative or its salt of the replacement of general formula (I) expression, contain aminoquinazolinone (thioketones) derivative of above-mentioned replacement or its salt agent for controlling noxious insect pests as active ingredient, and the method for using this agent for controlling noxious insect pests:
[wherein R is a hydrogen atom; Hydroxyl; Formyl radical; (C
1-12) alkyl; Halo (C
1-6) alkyl; Hydroxyl (C
1-6) alkyl; (C
2-6) alkenyl; (C
2-6) alkynyl; (C
1-6) alkoxyl group; Halo (C
1-6) alkoxyl group; (C
1-6) alkoxyl group (C
1-3) alkyl; (C
1-6) alkoxyl group (C
1-3) alkoxyl group (C
1-3) alkyl; (C
1-6) alkylthio; Halo (C
1-6) alkylthio; (C
1-6) alkyl sulphinyl; (C
1-6) alkyl sulphonyl; (C
1-6) alkylthio (C
1-3) alkyl; Two (C
1-6) alkoxyl group (C
1-3) alkyl, wherein (C
1-6) alkoxyl group can be identical or different; Unsubstituted amino (C
1-6) alkyl; Has one or two substituent substituted-amino (C
1-6) alkyl, wherein substituting group can be identical or different, is selected from (C
1-6) alkyl, halo (C
1-6) alkyl, (C
2-6) alkenyl and (C
2-6) alkynyl; Cyano group (C
1-6) alkyl; (C
1-6) alkyl-carbonyl; (C
1-6) alkoxy carbonyl; Hydroxycarbonyl group (C
1-3) alkyl; (C
1-6) alkoxy carbonyl (C
1-3) alkyl; Unsubstituted aminocarboxyl; Have one or two substituent substituted aminocarbonyl, wherein substituting group can be identical or different, is selected from (C
1-6) alkyl, (C
2-6) alkenyl and (C
2-6) alkynyl; (C
3-6) cycloalkyl (C
1-3) alkyl; Unsubstituted phenyl (C
1-3) alkyl; Have 1-5 substituent substituted-phenyl (C on the ring
1-3) alkyl, wherein substituting group can be identical or different, is selected from halogen atom, nitro, cyano group, (C
1-6) alkyl, halo (C
1-6) alkyl, (C
1-6) alkoxyl group, halo (C
1-6) alkoxyl group, (C
1-6) alkylthio and halo (C
1-6) alkylthio; Unsubstituted phenylcarbonyl group; Have 1-5 substituent substituted-phenyl carbonyl on the ring, wherein substituting group can be identical or different, is selected from halogen atom, nitro, cyano group, (C
1-6) alkyl, halo (C
1-6) alkyl, (C
1-6) alkoxyl group, halo (C
1-6) alkoxyl group, (C
1-6) alkylthio and halo (C
1-6) alkylthio; Unsubstituted thiophenyl; Have 1-5 substituent substituted benzene sulfenyl on the ring, wherein substituting group can be identical or different, is selected from halogen atom, nitro, cyano group, (C
1-6) alkyl, halo (C
1-6) alkyl, (C
1-6) alkoxyl group, halo (C
1-6) alkoxyl group, (C
1-6) alkylthio and halo (C
1-6) alkylthio; Unsubstituted phenyl sulfonyl; Have 1-5 substituent substituted phenyl sulfonyl base on the ring, wherein substituting group can be identical or different, is selected from halogen atom, nitro, cyano group, (C
1-6) alkyl, halo (C
1-6) alkyl, (C
1-6) alkoxyl group, halo (C
1-6) alkoxyl group, (C
1-6) alkylthio and halo (C
1-6) alkylthio; Unsubstituted phenyl (C
1-6) alkyl sulphonyl, have 1-5 substituent substituted-phenyl (C on the ring
1-6) alkyl sulphonyl, wherein substituting group can be identical or different, is selected from halogen atom, nitro, cyano group, (C
1-6) alkyl, halo (C
1-6) alkyl, (C
1-6) alkoxyl group, halo (C
1-6) alkoxyl group, (C
1-6) alkylthio and halo (C
1-6) alkylthio; The unsubstituted phenoxy carbonyl; Have 1-5 substituent substituent phenoxy carbonyl on the ring, wherein substituting group can be identical or different, is selected from halogen atom, nitro, cyano group, (C
1-6) alkyl, halo (C
1-6) alkyl, (C
1-6) alkoxyl group, halo (C
1-6) alkoxyl group, (C
1-6) alkylthio and halo (C
1-6) alkylthio, unsubstituted phenoxy (C
1-3) alkyl; Have 1-5 substituent substituent phenoxy (C on the ring
1-3) alkyl, wherein substituting group can be identical or different, is selected from halogen atom, nitro, cyano group, (C
1-6) alkyl, halo (C
1-6) alkyl, (C
1-6) alkoxyl group, halo (C
1-6) alkoxyl group, (C
1-6) alkylthio and halo (C
1-6) alkylthio; Unsubstituted phenyl (C
2-6) alkenyl; Have 1-5 substituent substituted-phenyl (C on the ring
2-6) alkenyl, wherein substituting group can be identical or different, is selected from halogen atom, nitro, cyano group, (C
1-6) alkyl, halo (C
1-6) alkyl, (C
1-6) alkoxyl group, halo (C
1-6) alkoxyl group, (C
1-6) alkylthio, halo (C
1-6) alkylthio and (C
1-2) alkylenedioxy group; Unsubstituted phenyl (C
2-6) alkynyl; Have 1-5 substituent substituted-phenyl (C on the ring
2-6) alkynyl, wherein substituting group can be identical or different, is selected from halogen atom, nitro, cyano group, (C
1-6) alkyl, halo (C
1-6) alkyl, (C
1-6) alkoxyl group, halo (C
1-6) alkoxyl group, (C
1-6) alkylthio, halo (C
1-6) alkylthio and (C
1-2) alkylenedioxy group; Unsubstituted phenyl (C
2-4) alkynyl (C
1-3) alkyl; Have 1-5 substituent substituted-phenyl (C on the ring
2-4) alkynyl (C
1-3) alkyl, wherein substituting group can be identical or different, is selected from halogen atom, nitro, cyano group, (C
1-6) alkyl, halo (C
1-6) alkyl, (C
1-6) alkoxyl group, halo (C
1-6) alkoxyl group, (C
1-6) alkylthio, halo (C
1-6) alkylthio and (C
1-2) alkylenedioxy group; 1,3-dioxolane-2-base (C
1-3) alkyl; Or phthaloyl imino (C
1-6) alkyl,
R
1Be to have 1-3 heteroatomic 5-or 6-unit heterocycle, wherein heteroatoms can be identical or different, is selected from Sauerstoffatom, and sulphur atom and nitrogen-atoms, described heterocycle can have 1-5 substituting group, and wherein substituting group can be identical or different, is selected from halogen atom, cyano group, (C
1-6) alkyl, halo (C
1-6) alkyl and (C
1-6) alkoxyl group, and assorted ring nitrogen can form the N-oxide groups,
Y is Sauerstoffatom or sulphur atom,
Z is
-N＝C(R
2)-
(R wherein
2Be hydrogen atom, (C
1-6) alkyl or halo (C
1-6) alkyl), or
-N(R
3)-CH(R
2)-
(R wherein
2Define as above, and R
3Be hydrogen atom, (C
1-6) alkyl, formyl radical, (C
1-3) alkyl-carbonyl or halo (C
1-3) alkyl-carbonyl),
X can be identical or different, is bromine atoms, the iodine atom; Hydroxyl; Cyano group; (C
1-6) alkyl; Halo (C
1-10) alkyl; (C
2-6) alkenyl; Halo (C
2-6) alkenyl; (C
2-6) alkynyl; (C
1-6) alkoxyl group; Halo (C
1-6) alkoxyl group; (C
1-6) alkylthio; Halo (C
1-6) alkylthio; (C
1-6) alkyl sulphinyl; Halo (C
1-6) alkyl sulphinyl; (C
1-6) alkyl sulphonyl; Halo (C
1-6) alkyl sulphonyl; Halo (C
1-6) halogenated alkoxy (C
1-6) alkoxyl group; Carboxyl; (C
1-6) carbalkoxy; Unsubstituted aminocarboxyl; Have one or two substituent substituted aminocarbonyl, wherein substituting group can be identical or different, is selected from (C
1-6) alkyl, (C
2-6) alkenyl and (C
2-6) alkynyl; Carboxyl (C
1-6) alkyl; (C
1-6) carbalkoxy (C
1-3) alkyl; Unsubstituted aminocarboxyl (C
1-3) alkyl; Has one or two substituent substituted aminocarbonyl (C
1-3) alkyl, wherein substituting group can be identical or different, is selected from (C
1-6) alkyl, (C
2-6) alkenyl and (C
2-6) alkynyl; Sulfonic group; Unsubstituted amino-sulfonyl; (C
1-6) the alkoxyl group alkylsulfonyl; Have one or two substituent substituted-amino alkylsulfonyl, wherein substituting group can be identical or different, is selected from (C
1-6) alkyl, (C
2-6) alkenyl and (C
2-6) alkynyl; Unsubstituted phenyl; Have 1-5 substituent substituted-phenyl on the ring, wherein substituting group can be identical or different, is selected from halogen atom, nitro, cyano group, (C
1-6) alkyl, halo (C
1-6) alkyl, (C
1-6) alkoxyl group, halo (C
1-6) alkoxyl group, (C
1-6) alkylthio, halo (C
1-6) alkylthio, (C
1-6) alkoxyl group alkylsulfonyl and have one or two substituent substituted-amino alkylsulfonyl, wherein substituting group can be identical or different, is selected from (C
1-6) alkyl, (C
2-6) alkenyl and (C
2-6) alkynyl; Unsubstituted phenyl (C
1-3) alkyl; Have 1-5 substituent substituted-phenyl (C on the ring
1-3) alkyl, wherein substituting group can be identical or different, is selected from halogen atom, nitro, cyano group, (C
1-6) alkyl, halo (C
1-6) alkyl, (C
1-6) alkoxyl group, halo (C
1-6) alkoxyl group, (C
1-6) alkylthio and halo (C
1-6) alkylthio; Unsubstituted phenoxy; Have 1-5 substituent substituent phenoxy on the ring, wherein substituting group can be identical or different, is selected from halogen atom, nitro, cyano group, (C
1-6) alkyl, halo (C
1-6) alkyl, (C
1-6) alkoxyl group, halo (C
1-6) alkoxyl group, (C
1-6) alkylthio and halo (C
1-6) alkylthio; Unsubstituted pyridine oxygen base; Have one or more substituent substituted pyridines oxygen bases on the ring, wherein substituting group can be identical or different, is selected from halogen atom, nitro, cyano group, (C
1-6) alkyl, halo (C
1-6) alkyl, (C
1-6) alkoxyl group, halo (C
1-6) alkoxyl group, (C
1-6) alkylthio and halo (C
1-6) alkylthio; And n is 0 to 4 integer].
The invention still further relates to by midbody compound general formula (II) expression, the preparation said derivative:
[wherein, X can be identical or different, is bromine atoms, the iodine atom; Hydroxyl; Cyano group; (C
1-6) alkyl; Halo (C
1-10) alkyl; (C
2-6) alkenyl; Halo (C
2-6) alkenyl; (C
2-6) alkynyl; (C
1-6) alkoxyl group; Halo (C
1-6) alkoxyl group; (C
1-6) alkylthio; Halo (C
1-6) alkylthio; (C
1-6) alkyl sulphinyl; Halo (C
1-6) alkyl sulphinyl; (C
1-6) alkyl sulphonyl; Halo (C
1-6) alkyl sulphonyl; Halo (C
1-6) halogenated alkoxy (C
1-6) alkoxyl group; Carboxyl; (C
1-6) carbalkoxy; Unsubstituted aminocarboxyl; Have one or two substituent substituted aminocarbonyl, wherein substituting group can be identical or different, is selected from (C
1-6) alkyl, (C
2-6) alkenyl and (C
2-6) alkynyl; Carboxyl (C
1-6) alkyl; (C
1-6) carbalkoxy (C
1-3) alkyl; Unsubstituted aminocarboxyl (C
1-3) alkyl; Has one or two substituent substituted aminocarbonyl (C
1-3) alkyl, wherein substituting group can be identical or different, is selected from (C
1-6) alkyl, (C
2-6) alkenyl and (C
2-6) alkynyl; Sulfonic group; (C
1-6) the alkoxyl group alkylsulfonyl; Have hydrogen atom, (C on the nitrogen-atoms
1-6) alkyl, (C
2-6) alkenyl or (C
2-6) amino-sulfonyl of alkynyl; Unsubstituted phenyl; Have 1-5 substituent substituted-phenyl on the ring, wherein substituting group can be identical or different, is selected from halogen atom, nitro, cyano group, (C
1-6) alkyl, halo (C
1-6) alkyl, (C
1-6) alkoxyl group, halo (C
1-6) alkoxyl group, (C
1-6) alkylthio and halo (C
1-6) alkylthio; Unsubstituted phenyl (C
1-3) alkyl; Have 1-5 substituent substituted-phenyl (C on the ring
1-3) alkyl, wherein substituting group can be identical or different, is selected from halogen atom, nitro, cyano group, (C
1-6) alkyl, halo (C
1-6) alkyl, (C
1-6) alkoxyl group, halo (C
1-6) alkoxyl group, (C
1-6) alkylthio and halo (C
1-6) alkylthio; Unsubstituted phenoxy; Have 1-5 substituent substituent phenoxy on the ring, wherein substituting group is selected from halogen atom with identical or different, nitro, cyano group, (C
1-6) alkyl, halo (C
1-6) alkyl, (C
1-6) alkoxyl group, halo (C
1-6) alkoxyl group, (C
1-6) alkylthio and halo (C
1-6) alkylthio; Unsubstituted pyridine oxygen base; Have one or more substituent substituted pyridines oxygen bases on the ring, wherein substituting group can be identical or different, is selected from halogen atom, nitro, cyano group, (C
1-6) alkyl, halo (C
1-6) alkyl, (C
1-6) alkoxyl group, halo (C
1-6) alkoxyl group, (C
1-6) alkylthio and halo (C
1-6) alkylthio; N is 0 to 4 integer; And Y is Sauerstoffatom or sulphur atom].
Contain substituted-amino quinazolinone (thioketones) derivative of general formula (I) expression or its salt as the agent for controlling noxious insect pests of the present invention of active ingredient when the low dosage to greenhouse whitefly (
Trialeurodes Vaporariorum) wait and have outstanding insecticidal effect, and the similar compound that routinizes of chemical structure does not have insecticidal effect to this insect.Therefore, compare with the compound that routinizes, substituted-amino quinazolinone of the present invention (thioketones) derivative is outstanding agent for controlling noxious insect pests.
In the substituent definition of general formula of the present invention (I) substituted-amino quinazolinone (thioketones) derivative, " halogen atom " refers to the chlorine atom, bromine atoms, iodine atom or fluorine atom.Term " (C
1-12) " refer to 1-12 carbon atom.Term " (C
1-12) alkyl " refer to the straight or branched alkyl of 1-12 carbon atom, as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl, n-undecane base, dodecyl etc.Term " halo (C
1-10) alkyl " refer to have substituted straight chain or the branched-chain alkyl of one or more identical or different halogen atoms as a substituent 1-10 carbon atom, as trifluoromethyl, pentafluoroethyl group, seven fluoropropyls etc.Term " (C
2-6) alkenyl " refer to have the straight or branched alkenyl of 2-6 carbon atom of one or more pairs of keys.Term " halo (C
2-6) alkenyl " refer to have substituted straight chain or the branched alkenyl of one or more identical or different halogen atoms as a substituent 2-6 carbon atom.Term " (C
2-6) alkynyl " refer to have the straight or branched alkynyl of 2-6 carbon atom of one or more three keys.Term " halo (C
2-6) alkynyl " refer to have substituted straight chain or the alkynyl group of one or more identical or different halogen atoms as a substituent 2-6 carbon atom.Term " have one or more can be identical or different and be selected from Sauerstoffatom, the heteroatomic 5-of sulphur atom and nitrogen-atoms or 6-unit heterocycle " refers to following any 5-or 6-unit heterocycle, as furans, and thiophene, the pyrroles, azoles, thiazole, pyrazoles, imidazoles, 1,2, the 3-thiadiazoles, 1,2,4-thiadiazoles, 1,2,5-thiadiazoles, 1,3, the 4-thiadiazoles, 1,2, the 4-triazole, pyridine, pyridazine, pyrimidine, pyrazine, tetramethyleneimine, piperidines, morpholine, thiomorpholine, dithiolane, dithiane, piperazine, dioxolane, imidazolidine, tetrahydrofuran (THF) etc.
The substituting group of substituted-amino quinazolinone (thioketones) derivative of general formula (I) expression is preferred: R is a hydrogen atom, formyl radical, (C
1-6) alkyl, (C
2-6) alkenyl, (C
2-6) alkynyl, (C
1-6) alkyl-carbonyl, (C
1-6) alkoxy carbonyl, (C
1-6) alkylthio, halo (C
1-6) alkylthio, phenylcarbonyl group, the phenylcarbonyl group of replacement, the phenyl (C of replacement
1-6) alkyl, the phenyl (C of replacement
2-6) alkenyl, the phenyl (C of replacement
2-6) alkynyl; R
1Be pyridyl, 3-pyridyl particularly; Y is Sauerstoffatom or sulphur atom; Z is the following formula group
-N(R
3)-CH(R
2)-
(R wherein
2And R
3Respectively be hydrogen atom or (C
1-6) alkyl); X is a bromine atoms, iodine atom, halo (C
1-6) alkyl, halo (C
1-6) alkoxyl group, halo (C
1-6) alkylthio, halo (C
1-6) alkyl sulphinyl, halo (C
1-6) alkyl sulphonyl or phenyl); And the integer of the preferred 0-2 of n.
The salt of substituted-amino quinazolinone (thioketones) derivative of general formula (I) expression can be and the mineral acid example hydrochloric acid, sulfuric acid, the salt that nitric acid etc. form and with alkali metal atom such as sodium, the salt that potassium etc. form.
Intermediate formula (II) compound that is used to prepare substituted-amino quinazolinone (thioketones) derivative of general formula (I) expression can prepare by following any method.
The preparation method 1
Wherein X and n define as above, R
4Be (C
1-6) alkyl, Hal is a halogen atom.
In the presence of inert solvent, make the reaction of above-mentioned general formula (III) compound and hydrazine hydrate, can prepare general formula (II-1) compound.
This reaction can be used any inert solvent, as long as it does not produce obvious suppression to reaction process.The example of solvent is an alcohol, as methyl alcohol, and ethanol, propyl alcohol, butanols etc., halohydrocarbon, as methylene dichloride, chloroform, tetracol phenixin etc.; Aromatic hydrocarbon, as benzene, toluene, dimethylbenzene, monochloro benzene etc.; Nitrile, as acetonitrile, benzonitrile etc.; Cellosolve is as methylcyclohexane; Ether, as ether, diglyme, two alkane, tetrahydrofuran (THF) etc.; Acid amides, as dimethyl formamide, N,N-DIMETHYLACETAMIDE, 1,3-dimethyl-2-imidazolidone, 1-Methyl-2-Pyrrolidone, etc.; Methyl-sulphoxide; Tetramethylene sulfone; Water.These inert solvents both can use separately, also can mix use.
Suitable temperature of reaction is selected from room temperature to the boiling point of employed inert solvent, preferred room temperature to 90 ℃.
Because reaction is a reaction with same mole, so, although any in can excessive use reaction reagent uses equimolar general formula (III) compound and hydrazine hydrate just can satisfy reaction.The excessive hydrazine hydrate of preferred use.
Although the reaction times is depended on reaction scale, temperature of reaction etc., the scope in reaction times are several minutes to 48 hour.
After reaction finishes, can from the reaction mixture that contains required compound, required compound be separated by ordinary method, if desired, can be with the gained compound by recrystallization, purifying such as dry chromatography obtain required compound.
Above-mentioned general formula (III) compound can be by Collect.Czech.Chem.Commn. (Vol.55), 752 (1990) preparations.
The preparation method 2
R wherein
4, X, Y and n definition are as above.
2-1. general formula (VIII) → general formula (VI)
In the presence of inert solvent and catalyzer, make the reaction of general formula (VIII) compound and general formula (VII) compound can prepare general formula (VI) compound.
This reaction can be used, for example, and the inert solvent that preparation method 1 is cited.These inert solvents both can use separately, also can mix use.
Spendable catalyzer is mineral acid (for example hydrochloric acid and a sulfuric acid), acetate, tosic acid etc.The amount of employed catalyzer makes that the content of catalyzer is 0.001wt%-10wt% in the reactive system based on the weight of general formula (VIII) compound.
Because reaction is a reaction with same mole, so, although any in can excessive use reaction reagent uses equimolar general formula (VIII) compound and general formula (VII) compound just can satisfy reaction.
Suitable temperature of reaction is selected from room temperature to the boiling point of employed inert solvent, preferred room temperature to 90 ℃.
Although the reaction times is depended on reaction scale, temperature of reaction etc., the scope in reaction times are several minutes to 48 hour.
After reaction finishes, can handle the reaction mixture that contains required compound, obtain required compound thus by the method identical with preparation method 1.
General formula (VIII) compound can be buied by market, maybe can make by the phenyl aldehyde of nitrated replacement.In addition, general formula (VIII) compound also can be by Journal of Chemical Society, and 1927, the described method preparation of pp.2375-2378.
2-2. general formula (VI) → logical formula V
Exist or do not exist under the situation of inert solvent,, can prepare logical formula V compound by reduce general formula (VI) compound or with reductive agent by catalytic reduction.
The example of spendable reductive agent is a metal hydride as, NaBH
3CN, LiBH
3CN etc. and reductive agent such as BH
3, etc.The amount of employed reductive agent can be suitably in 1 mole of every mole of general formula (VI) compound (calculating) selection in the scope of excessive mole number with mole number as the hydride of reductive agent.
This reaction can be used any inert solvent, as long as it does not produce obvious suppression to reaction process.The example of solvent is an alcohol, as methyl alcohol, and ethanol, propyl alcohol, butanols etc.; Cellosolve is as methylcyclohexane etc.; Ether, as ether, diglyme, two alkane, tetrahydrofuran (THF) etc.; Ester is as ethyl acetate etc.; Acid amides, as dimethyl formamide, N,N-DIMETHYLACETAMIDE, 1,3-dimethyl-2-imidazolidone, 1-Methyl-2-Pyrrolidone etc.; Methyl-sulphoxide; Tetramethylene sulfone; And water.These inert solvents both can use separately, also can mix use.
This reaction can be 1-7 in the pH scope, carries out under the acidity of preferred 4-6 or the neutrallty condition.By add hydrochloric acid in reactive system, the pH value can be suitably regulated in Hydrogen bromide or similarly acid.
Temperature of reaction is selected from 0 ℃ of boiling point to solvent, and preferable range is a room temperature to 70 ℃.
Although the reaction times is depended on reaction scale, temperature of reaction etc., the scope in reaction times are several minutes to 48 hour.
After reaction finishes, can handle the reaction mixture that contains required compound, obtain required compound thus by the method identical with preparation method 1.
When reduction reaction was catalytic reduction, it can be by for example Shin Jikken Kagaku Koza, Vol.15-11, and Maruzen Co., the described method of Ltd. is carried out.
In this case, the example of available inert solvent is an alcohol, as methyl alcohol, and ethanol, propyl alcohol, butanols etc.; Cellosolve is as methylcyclohexane etc.; Ether, as ether, diglyme, two alkane, tetrahydrofuran (THF) etc.; Hydrocarbon, as hexane, hexanaphthene etc.; Lipid acid or its ester, as acetate, ethyl acetate etc.; Acid amides, as dimethyl formamide, N,N-DIMETHYLACETAMIDE, 1,3-dimethyl-2-imidazolidone, 1-Methyl-2-Pyrrolidone etc.; And urea, as tetramethyl-urea etc.These inert solvents both can use separately, also can mix use.
Employed catalyzer can be typical catalyzer in the catalytic reduction in this reduction reaction, as palladium-carbon, and palladium black, platinum dioxide, Raney nickel, etc.With respect to general formula (VI) compound, the amount of employed catalyzer suitably is selected from 0.1% molar equivalent to 5% molar equivalent, and preferred 0.5% molar equivalent is to 1% molar equivalent.
The scope of hydrogen pressure is that atmosphere is pressed onto 300 normal atmosphere during reaction, and preferred atmosphere is pressed onto 50 normal atmosphere.
Temperature of reaction suitably is selected from room temperature to the boiling point of employed inert solvent, and preferable range is a room temperature to 70 ℃.
Although the reaction times is depended on reaction scale, temperature of reaction is a several minutes to 48 hour etc., the scope in reaction times.
After reaction finishes, can handle the reaction mixture that contains required compound, by than obtaining required compound by method identical when using reductive agent.
2-3. logical formula V → general formula (IV)
In the presence of inert solvent, and have or alkali-free in the presence of, make logical formula V compound and 1,1 '-carbonyl diurethane-1H-imidazoles (CDI), alkoxy carbonyl halogenide, phosgene or thiophosgene are reacted, and can prepare general formula (IV) compound.
This example that reacts spendable inert solvent is an ether, as ether, and diglyme, two alkane, tetrahydrofuran (THF), etc., and aromatic hydrocarbon, as benzene, toluene, dimethylbenzene, etc.These inert solvents both can use separately, also can mix use.
Both can use mineral alkali also can use organic bases, the example of mineral alkali is the oxyhydroxide of basic metal and alkaline-earth metal and carbonate [sodium hydroxide for example, potassium hydroxide, magnesium hydroxide, yellow soda ash, sodium bicarbonate and salt of wormwood], the example of organic bases is triethylamine and pyridine.When using CDI as reaction reagent, this reaction can be carried out under the situation of alkali not having.
Every mole of logical formula V compound uses 2 moles or more alkali.
Temperature of reaction suitably is selected from room temperature to the boiling point of employed inert solvent, and preferable range is a room temperature to 100 ℃.
Although the reaction times is depended on reaction rule film, temperature of reaction is a several minutes to 48 hour etc., the scope in reaction times.
After reaction finishes, can handle the reaction mixture that contains required compound, obtain required compound thus by the method identical with preparation method 1.
2-4. general formula (IV) → general formula (II)
In the presence of inert solvent, and under alkaline condition hydrolysis general formula (IV) compound, can prepare general formula (II) compound.
This example that reacts spendable inert solvent is an alcohol, as methyl alcohol, and ethanol, propyl alcohol, butanols etc.; Aromatic hydrocarbon, as benzene, toluene, dimethylbenzene etc.; Ether, as ether, diglyme, two alkane, tetrahydrofuran (THF) etc.; And water.These inert solvents both can use separately, also can mix use.
Alkali can use the oxyhydroxide of basic metal and alkaline-earth metal, as sodium hydroxide, and potassium hydroxide, magnesium hydroxide, etc.
According to R
4Alkyl, this reaction also can be carried out under acidic conditions, can use organic acid or mineral acid, as trifluoroacetic acid or hydrochloric acid.
Temperature of reaction suitably is selected from 0 ℃ of boiling point to employed inert solvent.
Although the reaction times is depended on reaction scale, temperature of reaction is a several minutes to 48 hour etc., the scope in reaction times.
After reaction finishes, can handle the reaction mixture that contains required compound, obtain required compound thus by the method identical with preparation method 1.
Exemplary by preparation method 1 and 2 general formula (II) compounds that prepare is listed in table 1, but they are not limited to scope of the present invention.Table 1, in 3 to 4, " Ph " represents phenyl, " Pyr " represents pyridyl.
General formula (II)
Table 1
| No. | Xn | Y | Physical properties |
| II-1 II-2 II-3 II-4 II-5 II-6 II-7 II-8 II-9 II-10 II-11 II-12 II-13 II-14 II-15 II-16 II-17 II-18 II-19 II-20 II-21 II-22 II-23 II-24 | 5-OH 6-OH 7-OH 8-OH 5-Br 6-Br 7-Br 8-Br 5-I 6-I 7-I 8-I 5-CF 3 6-CF 3 7-CF 3 8-CF 3 5-C 2F 5 6-C 2F 5 7-C 2F 5 8-C 2F 5 5-i-C 3F 7 6-i-C 3F 7 7-i-C 3F 7 8-i-C 3F 7 | O O O O O O O O O O O O O O O O O O O O O O O O | M.p.202.3-205.0 ℃ m.p.155-157.7 ℃ m.p.178.4-183.5 ℃ m.p.147.6-149.5 ℃ in crystal crystal crystal crystal crystal |
Table 1 (continuing)
| No. | Xn | Y | Physical properties |
| II-25 II-26 II-27 II-28 II-29 II-30 II-31 II-32 II-33 II-34 II-35 II-36 II-37 II-38 II-39 II-40 II-41 II-42 II-43 II-44 II-45 II-46 II-47 II-48 | 5-n-C 6F 13 6-n-C 6F 13 7-n-C 6F 13 8-n-C 6F 13 5-OCF 3 6-OCF 3 7-OCF 3 8-OCF 3 5-OCH 2-Ph 6-OCH 2-Ph 7-OCH 2-Ph 8-OCH 2-Ph 5-OCHF 2 6-OCHF 2 7-OCHF 2 8-OCHF 2 5-SCF 3 6-SCF 3 7-SCF 3 8-SCF 3 5-SC 2F 5 6-SC 2F 5 7-SC 2F 5 8-SC 2F 5 | O O O O O O O O O O O O O O O O O O O O O O O O | Crystal m.p.181.5-184.0 ℃ of crystal crystal crystal |
Table 1 (continuing)
| No. | Xn | Y | Physical properties |
| II-49 II-50 II-51 II-52 II-53 II-54 II-55 II-56 II-57 II-58 II-59 II-60 II-61 II-62 II-63 II-64 II-65 II-66 II-67 II-68 II-69 II-70 II-71 II-72 | 5-S-i-C 3F 7 6-S-i-C 3F 7 7-S-i-C 3F 7 8-S-i-C 3F 7 5-SOCF 3 6-SOCF 3 7-SOCF 3 8-SOCF 3 5-SO 2CF 3 6-SO 2CF 3 7-SO 2CF 3 8-SO 2CF 3 5-SOC 2F 5 6-SOC 2F 5 7-SOC 2F 5 8-SOC 2F 5 5-SO 2C 2F 5 6-SO 2C 2F 5 7-SO 2C 2F 5 8-SO 2C 2F 5 5-SO-i-C 3F 7 6-SO-i-C 3F 7 7-SO-i-C 3F 7 8-SO-i-C 3F 7 | O O O O O O O O O O O O O O O O O O O O O O O O | m.p.71.2-73.5℃ |
Table 1 (continuing)
| No. | Xn | Y | Physical properties |
| II-73 II-74 II-75 II-76 II-77 II-78 II-79 II-80 II-81 II-82 II-83 II-84 II-85 II-86 II-87 II-88 II-89 II-90 II-91 II-92 II-93 II-94 II-95 II-96 | 5-SO 2-i-C 3F 7 6-SO 2-i-C 3F 7 7-SO 2-i-C 3F 7 8-SO 2-i-C 3F 7 5-COOC 2H 5 6-COOC 2H 5 7-COOC 2H 5 8-COOC 2H 5 5-COOH 6-COOH 7-COOH 8-COOH 5-Ph 6-Ph 7-Ph 8-Ph 5-(p-Cl-Ph) 6-(p-Cl-Ph) 7-(p-Cl-Ph) 8-(p-Cl-Ph) 5-O-Ph 6-O-Ph 7-O-Ph 8-O-Ph | O O O O O O O O O O O O O O O O O O O O O O O O |
Table 1 (continuing)
| No. | Xn | Y | Physical properties |
| II-97 II-98 II-99 II-100 II-101 II-102 II-103 II-104 II-105 II-106 II-107 II-108 | 5-n-C 4H 9 6-n-C 4H 9 7-n-C 4H 9 8-n-C 4H 9 5-OCF 2CHF 2 6-OCF 2CHF 2 7-OCF 2CHF 2 8-OCF 2CHF 2 6-OCF 2CHFOCF 3 6-OCH(CF 3) 2 6-O-(m-CF 3-Ph) 6-O-(3-Cl-5-CF 3 -2-Pyr) | O O O O O O O O O O O O | M.p.194.8 ℃ of crystal m.p.238.8-241.0 ℃ m.p.204.7-207.9 ℃ crystal |
Table 2 indicator gauge 1 compound N MR data.
Table 2
| No. | 1H-NMR[DMSO-d 6/TMS，δ(ppm)] |
| II-1 II-2 II-3 II-4 II-6 II-18 II-26 II-33 II-36 II-38 II-105 II-108 | 4.36(2H，s)，4.65(2H，br)，6.20(1H，d)，6.34(1H，d)， 6.89(1H，t)，9.12(1H，br)，9.62(1H，s). 4.45(2H，s)，4.65(2H，s)，6.51-6.63(3H，m)， 9.00(1H，s)， 9.60(1H，brs). 4.48(2H，s)，4.65(2H，s)，6.23-6.35(2H，m)， 6.85(1H，d)，9.05(1H，s)，9.63(1H，s) 4.46(2H，s)，4.65(2H，s)，6.57(1H，d)，6.64- 6.74(2H，m)，7.95(1H，d)，9.60(1H，brs). 4.48(2H，s)，4.66(2H，s)，6.74(1H，m)，7.18(1H，m)， 7.30(1H，m)，9.43(1H，s). 4.56(2H，s)，4.70(2H，s)，6.95(1H，d)，7.40- 7.50(2H，m)，9.83(1H，s). 4.56(2H，s)，4.70(2H，s)，6.94(1H，d)，7.43- 7.48(2H，m)，9.74(1H，s). 4.48(2H，s)，4.69(2H，s)，5.00(2H，s)，6.30(1H，d)， 6.45(1H，d)，7.05(1H，t)，7.25-7.40(6H，m). 4.48(2H，s)，4.68(2H，s)，5.19(2H，s)，6.71(1H，d)， 6.82(1H，t)，6.92(1H，d)，7.30-7.40(3H，m)， 7.51(2H，d)，8.18(1H，s). 4.48(2H，s)，4.65(2H，s)，6.76-6.79(1H，d，J＝8.7Hz)， 6.95-7.00(2H，m)，6.80-7.30(1H，t，J＝7.46)， 9.37(1H，s). 4.88(2H，s)，4.64(2H，s)，6.79(1H，d，J＝11.6Hz)， 7.00(1H，s)，7.06(1H，m)，7.23(1H，t，J＝4Hz)， 9.43(1H，s). 4.46(2H，s)，4.65(2H，s)，6.80(1H，d，J＝11.2Hz)， 7.01(2H，m)，8.48(1H，s)，8.52(1H，s)，9.38(1H，s). |
Aminoquinazolinone (thioketones) derivative of general formula of the present invention (I) expression or the preparation method's of its salt exemplary diagram is as follows.
The preparation method 3
R wherein, R
1, R
2, R
3, X, n, Y and Hal define as above, but R and R
3Can not be hydrogen atom.
3-1. general formula (II) → general formula (I-1)
In the presence of inert solvent and catalyzer,, can prepare general formula (I-1) aminoquinazolinone (thioketones) derivative by making the reaction of general formula (II) compound and general formula (X) compound.
In this reaction, can be by preparing the purpose compound with the described identical mode of preparation method 2-1.
3-2. general formula (I-1) → general formula (I-3)
Be with or without inert solvent and alkali in the presence of, by make general formula (I-1) aminoquinazolinone (thioketones) derivative and general formula (IX) compound the reaction, can prepare general formula (I-3) aminoquinazolinone (thioketones) derivative.
The inert solvent that this reaction is used can for, for example, the inert solvent that preparation method 1 enumerates.
Both can use mineral alkali also can use organic bases.Except that mineral alkali and organic bases that preparation method 2-3 enumerates, also can use alcoholate such as CH
3ONa, C
2H
5ONa, t-C
4H
9ONa, CH
3OK, C
2H
5OK, t-C
4H
9OK, etc. and alkalimetal hydride such as NaH, etc.The appropriate amount of the employed alkali of every mole of general formula (I-1) aminoquinazolinone (thioketones) derivative is 1 mole and arrives excessive mole number.
Temperature of reaction can be selected from 0 ℃ of boiling point to employed inert solvent, and preferable range is a room temperature to 70 ℃.
Although the reaction times is depended on reaction scale, temperature of reaction is a several minutes to 48 hour etc., the scope in reaction times.
After reaction finishes, can handle the reaction mixture that contains required compound, obtain required compound thus by the method identical with preparation method 1.
3-3. general formula (I-1) → general formula (I-2)
In this reaction, can be by preparing the purpose compound with the described identical mode of preparation method 2-2.
3-4. general formula (I-2) → general formula (I-4)
Be with or without inert solvent and alkali in the presence of, by make general formula (I-2) aminoquinazolinone (thioketones) derivative and general formula (IX) compound the reaction, can prepare general formula (I-4) aminoquinazolinone (thioketones) derivative.
In this reaction, can be by preparing the purpose compound with the described identical mode of preparation method 3-2.
3-5. general formula (I-4) → general formula (I-5)
Be with or without inert solvent and alkali in the presence of, by make general formula (I-4) aminoquinazolinone (thioketones) derivative and general formula (XI) compound the reaction, can prepare general formula (I-5) aminoquinazolinone (thioketones) derivative.
In this reaction, can be by preparing the purpose compound with the described identical mode of preparation method 3-2.
3-6. general formula (I-3) → general formula (I-5)
In this reaction, can be by preparing the purpose compound with the described identical mode of preparation method 2-2.
The exemplary of general formula of the present invention (I) aminoquinazolinone (thioketones) derivative or its salt is listed in table 3 and 4, but they are not limited to scope of the present invention.
Following substituting group is represented in abbreviation in table 3 and the table 4:
C: alicyclic alkyl,
Ph: phenyl,
Q
1: the 2-pyridyl,
Q
2: the 3-pyridyl,
Q
3: the 4-pyridyl,
Q
4: 2-pyridyl-N-oxide-base,
Q
5: 3-pyridyl-N-oxide-base,
Q
6: 4-pyridyl-N-oxide-base,
Q
7: thiazole-5-base,
Q
8: furans-2-base,
Q
9: 1,3-dioxolane-2-base,
Q
10: phthalic imidine-1-base,
Q
11: thiophene-2-base,
Q
12: 5-chloro-1,3-dimethyl pyrazole-4-base,
Table 3 (except that the group that particularly points out, R
1=Q
2, R
2=H, Y=Q.)
| No. | R | Xn | Physical properties |
| 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 | H H H H H H H H H H H H H H H H H H H H H H H H | 5-OH 6-OH 7-OH 8-OH 5-Br 6-Br 7-Br 8-Br 5-I 6-I 7-I 8-I 5-CF 3 6-CF 3 7-CF 3 8-CF 3 5-C 2F 5 6-C 2F 5 7-C 2F 5 8-C 2F 5 5-i-C 3F 7 6-i-C 3F 7 7-i-C 3F 7 8-i-C 3F 7 | m.p.293-295℃ m.p.＞300℃ m.p.＞300℃ m.p.＞300℃ m.p.227.6-286.7℃ m.p.298-300℃ m.p.＞300℃ |
Table 3 (continuing)
| No. | R | Xn | Physical properties |
| 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 | H H H H H H H H H H H H H H H H H H H H H H H H | 5-n-C 6F 13 6-n-C 6F 13 7-n-C 6F 13 8-n-C 6F 13 5-OCF 3 6-OCF 3 7-OCF 3 8-OCF 3 5-CH 2-Ph 6-CH 2-Ph 7-CH 2-Ph 8-CH 2-Ph 5-OCHF 2 6-OCHF 2 7-OCHF 2 8-OCHF 2 5-SCF 3 6-SCF 3 7-SCF 3 8-SCF 3 5-SC 2F 5 6-SC 2F 5 7-SC 2F 5 8-SC 2F 5 | m.p.＞300℃ m.p.264.0-266.0℃ m.p.260.1-264.5℃ |
Table 3 (continuing)
| No. | R | Xn | Physical properties |
| 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65 66 67 68 69 70 71 72 | H H H H H H H H H H H H H H H H H H H H H H H H | 5-S-i-C 3F 7 6-S-i-C 3F 7 7-S-i-C 3F 7 8-S-i-C 3F 7 5-SOCF 3 6-SOCF 3 7-SOCF 3 8-SOCF 3 5-SO 2CF 3 6-SO 2CF 3 7-SO 2CF 3 8-SO 2CF 3 5-SOC 2F 5 6-SOC 2F 5 7-SOC 2F 5 8-SOC 2F 5 5-SO 2C 2F 5 6-SO 2C 2F 5 7-SO 2C 2F 5 8-SO 2C 2F 5 5-SO-i-C 3F 7 6-SO-i-C 3F 7 7-SO-i-C 3F 7 8-SO-i-C 3F 7 | m.p.252.4-255.0℃ |
Table 3 (continuing)
| No. | R | Xn | Physical properties |
| 73 74 75 76 77 78 79 80 81 82 83 84 85 86 87 88 89 90 91 92 93 94 95 96 | H H H H H H H H H H H H H H H H H H H H H H H H | 5-SO 2-i-C 3F 7 6-SO 2-i-C 3F 7 7-SO 2-i-C 3F 7 8-SO 2-i-C 3F 7 5-COOC 2H 5 6-COOC 2H 5 7-COOC 2H 5 8-COOC 2H 5 5-COOH 6-COOH 7-COOH 8-COOH 5-Ph 6-Ph 7-Ph 8-Ph 5-(4-Cl-Ph) 6-(4-Cl-Ph) 7-(4-Cl-Ph) 8-(4-Cl-Ph) 5-O-Ph 6-O-Ph 7-O-Ph 8-O-Ph | m.p.274-278℃ m.p.250.9-253.8℃ m.p.276-278℃ |
Table 3 (continuing)
| No. | R | Xn | Physical properties |
| 97 98 99 100 101 102 103 104 105 106 107 108 109 110 111 112 113 114 115 116 117 118 119 120 | H H H H CH 3 CH 3 CH 3 CH 3 C 2H 5 C 2H 5 C 2H 5 C 2H 5 n-C 5H 11 n-C 5H 11 n-C 5H 11 n-C 5H 11 CH 2C≡CH CH 2C≡CH CH 2C≡CH CH 2C≡CH CH 2CH＝CH 2 CH 2CH＝CH 2 CH 2CH＝CH 2′ CH 2CH＝CH 2 | 5-n-C 4H 9 6-n-C 4H 9 7-n-C 4H 9 8-n-C 4H 9 5-I 6-I 7-I 8-I 5-I 6-I 7-I 8-I 5-I 6-I 7-I 8-I 5-I 6-I 7-I 8-I 5-I 6-I 7-I 8-I | m.p.181.4-185.3℃ m.p.191.5-194.5℃ nD 1.4126(28.5℃) m.p.214-217℃ m.p.162-164℃ |
Table 3 (continuing)
| No. | R | Xn | Physical properties |
| 121 122 123 124 125 126 127 128 129 130 131 132 133 134 135 136 137 138 139 140 141 142 143 144 | CH 2OC 2H 5 CH 2OC 2H 5 CH 2OC 2H 5 CH 2OC 2H 5 CH 2(4-Cl-Ph) CH 2(4-Cl-Ph) CH 2(4-Cl-Ph) CH 2(4-Cl-Ph) COCH 3 COCH 3 COCH 3 COCH 3 COC 2H 5 COC 2H 5 COC 2H 5 COC 2H 5 SO 2CH 3 SO 2CH 3 SO 2CH 3 SO 2CH 3 SO 2Ph SO 2Ph SO 2Ph SO 2Ph | 5-I 6-I 7-I 8-I 5-I 6-I 7-I 8-I 5-I 6-I 7-I 8-I 5-I 6-I 7-I 8-I 5-I 6-I 7-I 8-I 5-I 6-I 7-I 8-I | m.p.111.3-161.7℃ m.p.146-149℃ m.p.186-188℃ m.p.135-139℃ m.p.174-181℃ m.p.199-205℃ |
Table 3 (continuing)
| No. | R | Xn | Physical properties |
| 145 146 147 148 149 150 151 152 153 154 155 156 157 158 159 160 161 162 163 164 165 166 167 168 | H H H H CO-C-C 3H 5 CO-C-C 3H 5 CO-C-C 3H 5 CO-C-C 3H 5 H H H H H H H H H H H H H H H H | 5-OCF 2CHF 2 6-OCF 2CHF 2 7-OCF 2CHF 2 8-OCF 2CHF 2 5-I 6-I 7-I 8-I 5-(4-CH 3O-Ph) 6-(4-CH 3O-Ph) 7-(4-CH 3O-Ph) 8-(4-CH 3O-Ph) 5-(3-CH 3O-Ph 6-(3-CH 3O-Ph) 7-(3-CH 3O-Ph) 8-(3-CH 3O-Ph) 5-(3-NO 2-Ph) 6-(3-NO 2-Ph) 7-(3-NO 2-Ph) 8-(3-NO 2-Ph) 5-COOH 6-COOH 7-COOH 8-COOH | m.p.251.6-263.3℃ m.p.172-175℃ m.p.242℃ m.p.192-199℃ m.p.＞300℃ m.p.＞300℃ |
Table 3 (continuing)
| No. | R | Xn | Physical properties |
| 169 170 171 172 173 174 175 176 177 178 178.1 178.2 178.3 178.4 178.5 178.6 | H H H H H H H H H H H H H H H COOCH 3 | 5-COOCH 3 6-COOCH 3 7-COOCH 3 8-COOCH 3 5-CON(C 2H 5) 2 6-CON(C 2H 5) 2 7-CON(C 2H 5) 2 8-CON(C 2H 5) 2 6-Cl-7-CF 2H 6-C 3F 7-i | m.p.270.5-279.6℃ m.p.254.9-278.1℃ m.p.295℃ m.p.227.1-227.3℃ |
| (Q 2: N-picoline iodide salt) | |||
| 6-OCF 2CHFOCF 3 6-O-(3-Cl-5-CF 3- 2-Pyr) 6-O-(3-CF 3-Ph) 6-O-CH(CF 3) 2 6-F 6-C 3F 7-i | m.p.240.2-241.3℃ m.p.284.7-288.5℃ m.p.239.1-240.9℃ m.p.＞300℃ m.p.232.2-236.3℃ R 1＝Q 12 m.p.160-165℃ | ||
Table 4 (except that the group that particularly points out, R
2=H, Y=O and R
3=H.)
| No | R | R 1 | Xn | Physical properties |
| 179 180 181 182 183 184 185 186 187 188 189 190 191 192 193 194 195 196 197 198 199 200 201 202 | H H H H H H H H H H H H H H H H H H H H H H H H | Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 | 5-OH 6-OH 7-OH 8-OH 5-Br 6-Br 7-Br 8-Br 5-I 6-I 7-I 8-I 5-CF 3 6-CF 3 7-CF 3 8-CF 3 5-C 2F 5 6-C 2F 5 7-C 2F 5 8-C 2F 5 5-i-C 3F 7 6-i-C 3F 7 7-i-C 3F 7 8-i-C 3F 7 | m.p.223-225℃ m.p.258-259℃ m.p.177-180℃ m.p.＞300℃ m.p.191.0-193.1℃ m.p.159.4-161.0℃ |
Table 4 (continuing)
| No | R | R 1 | Xn | Physical properties |
| 203 204 205 206 207 208 209 210 211 212 213 214 215 216 217 218 219 220 221 222 223 224 225 226 | H H H H H H H H H H H H H H H H H H H H H H H H | Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 | 5-n-C 6F 13 6-n-C 6F 13 7-n-C 6F 13 8-n-C 6F 13 5-OCF 3 6-OCF 3 7-OCF 3 8-OCF 3 5-CH 2-Ph 6-CH 2-Ph 7-CH 2-Ph 8-CH 2-Ph 5-OCHF 2 6-OCHF 2 7-OCHF 2 8-OCHF 2 5-SCF 3 6-SCF 3 7-SCF 3 8-SCF 3 5-SC 2F 5 6-SC 2F 5 7-SC 2F 5 8-SC 2F 5 | m.p.153.9-164.7℃ nD 1.5233(22.6℃) m.p.129.7-130.2℃ |
Table 4 (continuing)
| No | R | R 1 | Xn | Physical properties |
| 227 228 229 230 231 232 233 234 235 236 237 238 239 240 241 242 243 244 245 246 247 248 249 250 | H H H H H H H H H H H H H H H H H H H H H H H H | Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 | 5-S-i-C 3F 7 6-S-i-C 3F 7 7-S-i-C 3F 7 8-S-i-C 3F 7 5-SOCF 3 6-SOCF 3 7-SOCF 3 8-SOCF 3 5-SO 2CF 3 6-SO 2CF 3 7-SO 2CF 3 8-SO 2CF 3 5-SOC 2F 5 6-SOC 2F 5 7-SOC 2F 5 8-SOC 2F 5 5-SO 2C 2F 5 6-SO 2C 2F 5 7-SO 2C 2F 5 8-SO 2C 2F 5 5-SO-i-C 3F 7 6-SO-i-C 3F 7 7-SO-i-C 3F 7 8-SO-i-C 3F 7 | m.p.50.3-53.1℃ |
Table 4 (continuing)
| No | R | R 1 | Xn | Physical properties |
| 251 252 253 254 255 256 257 258 259 260 261 262 263 264 265 266 267 268 269 270 271 272 273 274 | H H H H H H H H H H H H H H H H H H H H H H H H | Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 | 5-SO 2-i-C 3F 7 6-SO 2-i-C 3F 7 7-SO 2-i-C 3F 7 8-SO 2-i-C 3F 7 5-COOC 2H 5 6-COOC 2H 5 7-COOC 2H 5 8-COOC 2H 5 5-COOH 6-COOH 7-COOH 8-COOH 5-Ph 6-Ph 7-Ph 8-Ph 5-(4-Cl-Ph) 6-(4-Cl-Ph) 7-(4-Cl-Ph) 8-(4-Cl-Ph) 5-O-Ph 6-O-Ph 7-O-Ph 8-O-Ph |
Table 4 (continuing)
| No | R | R 1 | Xn | Physical properties |
| 275 276 277 278 279 280 281 282 283 284 285 286 287 288 289 290 291 292 293 294 295 296 297 | H H H H H H H H H H H H H CH 3 CH 3 CH 3 CH 3 C 2H 5 C 2H 5 C 2H 5 C 2H 5 COCH 3 COCH 3 | Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 5 Q 5 Q 5 Q 5 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 | 5-n-C 4H 9 6-n-C 4H 9 7-n-C 4H 9 8-n-C 4H 9 5-OCF 2CHF 2 6-OCF 2CHF 2 7-OCF 2CHF 2 8-OCF 2CHF 2 5-CF(CF 3) 2 6-CF(CF 3) 2 7-CF(CF 3) 2 8-CF(CF 3) 2 6-CF(CF 3) 2 5-OCF 3 6-OCF 3 7-OCF 3 8-OCF 3 5-OCF 3 6-OCF 3 7-OCF 3 8-OCF 3 5-OCF 3 6-OCF 3 | m.p.168.7-173.9℃ m.p.239.7-243.5℃ m.p.209.9-213.4℃ (R 3＝COCF 3) nD 1.5467(23.6℃) nD 1.5360(24.3℃) nD 1.5478(24.1℃) |
Table 4 (continuing)
| No | R | R 1 | Xn | Physical properties |
| 298 299 300 301 302 303 304 305 306 307 308 309 310 311 312 313 324 315 316 317 318 319 32O | COCH 3 COCH 3 COC 2H 5 COC 2H 5 COC 2H 5 COC 2H 5 CH 2CH＝CH 2 CH 2CH＝CH 2 CH 2CH＝CH 2 CH 2CH＝CH 2 CH 2C≡CH CH 2C≡CH CH 2C≡CH CH 2C≡CH CH(CH 3) 2 CH(CH 3) 2 CH(CH 3) 2 CH(CH 3) 2 H CH 2C≡CH CH 2C≡CH CH 2C≡CH CH 2C≡CH | Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 | 7-OCF 3 8-OCF 3 5-OCF 3 6-OCF 3 7-OCF 3 8-OCF 3 5-OCF 3 6-OCF 3 7-OCF 3 8-OCF 3 5-OCF 3 6-OCF 3 7-OCF 3 8-OCF 3 5-OCF 3 6-OCF 3 7-OCF 3 8-OCF 3 6-OCF 3 5-Br 6-Br 7-Br 8-Br | nD 1.5174(25.9℃) m.p.92.5℃ nD 1.5325(24.2℃) nD 1.5370(24.8℃) nD 1.5380(26.0℃) (R 3＝COC 2H 5) nD 1.5760(26.2℃) |
Table 4 (continuing)
| No | R | R 1 | Xn | Physical properties |
| 321 322 323 324 325 326 327 328 329 330 331 332 333 334 335 336 337 338 339 340 341 342 343 344 | CH 2SCH 3 CH 2SCH 3 CH 2SCH 3 CH 2SCH 3 C 2H 5 C 2H 5 C 2H 5 C 2H 5 i-C 3H 7 i-C 3H 7 i-C 3H 7 i-C 3H 7 COCH 3 COCH 3 COCH 3 COCH 3 COC 2H 5 COC 2H 5 COC 2H 5 COC 2H 5 CH 2-(4-Cl-Ph) CH 2-(4-Cl-Ph) CH 2-(4-Cl-Ph) CH 2-(4-Cl-Ph) | Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 | 5-Br 6-Br 7-Br 8-Br 5-Br 6-Br 7-Br 8-Br 5-Br 6-Br 7-Br 8-Br 5-Br 6-Br 7-Br 8-Br 5-Br 6-Br 7-Br 8-Br 5-Br 6-Br 7-Br 8-Br | nD 1.6030(27.0℃) nD 1.5974(26.9℃) nD 1.4680(28.0℃) nD 1.5930(27.2℃) nD 1.5861(26.8℃) nD 1.5885(27.3℃) |
Table 4 (continuing)
| No | R | R 1 | Xn | Physical properties |
| 345 346 347 348 349 350 351 352 353 354 355 356 357 358 359 360 361 362 363 364 365 366 367 368 | CO-Ph CO-Ph CO-Ph CO-Ph CH 3 CH 3 CH 3 CH 3 C 2H 5 C 2H 5 C 2H 5 C 2H 5 n-C 8H 17 n-C 8H 17 n-C 8H 17 n-C 8H 17 CH 2-(2-NO 2-Ph) CH 2-(2-NO 2-Ph) CH 2-(2-NO 2-Ph) CH 2-(2-NO 2-Ph) i-C 4H 9 i-C 4H 9 i-C 4H 9 i-C 4H 9 | Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 | 5-Br 6-Br 7-Br 8-Br 5-OCHF 2 6-OCHF 2 7-OCHF 2 8-OCHF 2 5-OCHF 2 6-OCHF 2 7-OCHF 2 8-OCHF 2 5-OCHF 2 6-OCHF 2 7-OCHF 2 8-OCHF 5-OCHF 2 6-OCHF 2 7-OCHF 2 8-OCHF 2 5-OCHF 2 6-OCHF 2 7-OCHF 2 8-OCHF 2 | m.p.＞300℃ nD 1.5613(27.9℃) nD 1.5354(26.4℃) nD 1.5590(25.8℃) nD 1.5917(27.9℃) nD 1.5557(26.4℃) |
Table 4 (continuing)
| No | R | R 1 | Xn | Physical properties |
| 369 370 371 372 373 374 375 376 377 378 379 380 381 382 383 384 385 386 387 388 389 390 391 392 | CH 2-(4-CH 3O-Ph) CH 2-(4-CH 3O-Ph) CH 2-(4-CH 3O-Ph) CH 2-(4-CH 3O-Ph) COCH 3 COCH 3 COCH 3 COCH 3 COC 2H 5 COC 2H 5 COC 2H 5 COC 2H 5 CO-i-C 3H 7 CO-i-C 3H 7 CO-i-C 3H 7 CO-i-C 3H 7 CO-Q 11 CO-Q 11 CO-Q 11 CO-Q 11 CH 3 CH 3 CH 3 CH 3 | Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 | 5-OCHF 2 6-OCHF 2 7-OCHF 2 8-OCHF 2 5-OCHF 2 6-OCHF 2 7-OCHF 2 8-OCHF 2 5-OCHF 2 6-OCHF 2 7-OCHF 2 8-OCHF 2 5-OCHF 2 6-OCHF 2 7-OCHF 2 8-OCHF 2 5-OCHF 2 6-OCHF 2 7-OCHF 2 8-OCHF 2 5-OCF 2CHF 2 6-OCF 2CHF 2 7-OCF 2CHF 2 8-OCF 2CHF 2 | nD 1.5668(26.5℃) nD 1.5503(26.1℃) nD 1.5470(26.2℃) nD 1.5196(28.3℃) m.p.148-155℃ nD 1.5320(26.2℃) |
Table 4 (continuing)
| No | R | R 1 | Xn | Physical properties |
| 393 394 395 396 397 398 399 400 401 402 403 404 405 406 407 408 409 410 411 412 413 414 415 416 | C 2H 5 C 2H 5 C 2H 5 C 2H 5 SO 2C 2H 5 SO 2C 2H 5 SO 2C 2H 5 SO 2C 2H 5 CH 2OCH 2-Ph CH 2OCH 2-Ph CH 2OCH 2-Ph CH 2OCH 2-Ph COOC 4H 9-t COOC 4H 9-t COOC 4H 9-t COOC 4H 9-t COCH 3 COCH 3 COCH 3 COCH 3 COC 2H 5 COC 2H 5 COC 2H 5 COC 2H 5 | Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 | 5-OCF 2CHF 2 6-OCF 2CHF 2 7-OCF 2CHF 2 8-OCF 2CHF 2 5-OCF 2CHF 2 6-OCF 2CHF 2 7-OCF 2CHF 2 8-OCF 2CHF 2 5-OCF 2CHF 2 6-OCF 2CHF 2 7-OCF 2CHF 2 8-OCF 2CHF 2 5-OCF 2CHF 2 6-OCF 2CHF 2 7-OCF 2CHF 2 8-OCF 2CHF 2 5-OCF 2CHF 2 6-OCF 2CHF 2 7-OCF 2CHF 2 8-OCF 2CHF 2 5-OCF 2CHF 2 6-OCF 2CHF 2 7-OCF 2CHF 2 8-OCF 2CHF 2 | nD 1.5239(26.7℃) nD 1.5309(26.0℃) nD 1.5486(26.2℃) nD 1.5103(26.2℃) nD 1.5262(25.8℃) nD 1.5266(25.9℃) |
Table 4 (continuing)
| No | R | R 1 | Xn | Physical properties |
| 417 418 419 420 421 422 423 424 425 426 427 428 429 430 431 432 433 434 435 436 437 438 | CH 2OCH 3 CH 2OCH 3 CH 2OCH 3 CH 2OCH 3 CH 2-Q 2 CH 2-Q 2 CH 2-Q 2 CH 2-Q 2 SO 2CH 3 SO 2CH 3 SO 2CH 3 SO 2CH 3 SO 2C 2H 5 SO 2C 2H 5 SO 2C 2H 5 SO 2C 2H 5 SO 2(4-CH 3-Ph) SO 2(4-CH 3-Ph) SO 2(4-CH 3-Ph) SO 2(4-CH 3-Ph) H H | Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 | 5-OCF 2CHF 2 6-OCF 2CHF 2 7-OCF 2CHF 2 8-OCF 2CHF 2 5-OCF 2CHF 2 6-OCF 2CHF 2 7-OCF 2CHF 2 8-OCF 2CHF 2 5-C 3F 7-i 6-C 3F 7-i 7-C 3F 7-i 8-C 3F 7-i 5-C 3F 7-i 6-C 3F 7-i 7-C 3F 7-i 8-C 3F 7-i 5-C 3F 7-i 6-C 3F 7-i 7-C 3F 7-i 8-C 3F 7-i 6-C 3F 7-i 6-C 3F 7-i | ND 1.5311 (23.9 ℃) nD 1.5560 (26.8 ℃) m.p.154-156 ℃ m.p.186-212 ℃ of ℃ m.p.65-75 of ℃ m.p.45-50 (hydrochloride) m.p.168-208.8 ℃ (vitriol) |
Table 4 (continuing)
| No | R | R 1 | Xn | Physical properties |
| 439 440 441 442 443 444 445 446 447 448 449 450 451 452 453 454 455 456 457 458 459 460 461 462 | CO-Ph CO-Ph CO-Ph CO-Ph COC 3H 7-i COC 3H 7-i COC 3H 7-i COC 3H 7-i COCH 3 COCH 3 COCH 3 COCH 3 COC 2H 5 COC 2H 5 COC 2H 5 COC 2H 5 COC 3H 7-n COC 3H 7-n COC 3H 7-n COC 3H 7-n CH 3 CH 3 CH 3 CH 3 | Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 | 5-C 3F 7-i 6-C 3F 7-i 7-C 3F 7-i 8-C 3F 7-i 5-C 3F 7-i 6-C 3F 7-i 7-C 3F 7-i 8-C 3F 7-i 5-C 3F 7-i 6-C 3F 7-i 7-C 3F 7-i 8-C 3F 7-i 5-C 3F 7-i 6-C 3F 7-i 7-C 3F 7-i 8-C 3F 7-i 5-C 3F 7-i 6-C 3F 7-i 7-C 3F 7-i 8-C 3F 7-i 5-C 3F 7-i 6-C 3F 7-i 7-C 3F 7-i 8-C 3F 7-i | m.p.161-165℃ nD 1.5051(22.1℃) m.p.132-134℃ m.p.108℃ nD 1.510(22.2℃) m.p.67-75℃ |
Table 4 (continuing)
| No | R | R 1 | Xn | Physical properties |
| 463 464 465 466 467 468 469 470 471 472 473 474 475 476 477 478 479 480 481 482 483 484 485 486 | C 2H 5 C 2H 5 C 2H 5 C 2H 5 COC 2H 5 COC 2H 5 COC 2H 5 COC 2H 5 H H H H COC 2H 5 COC 2H 5 COC 2H 5 COC 2H 5 H H H H H CH 2C≡CH CH 2OCH 3 CH 2SCH 3 | Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 | 5-C 3F 7-i 6-C 3F 7-i 7-C 3F 7-i 8-C 3F 7-i 5-F 6-F 7-F 8-F 5-COOC 2H 5 6-COOC 2H 5 7-COOC 2H 5 8-COOC 2H 5 5-CF 3 6-CF 3 7-CF 3 8-CF 3 5-C 2F 5 6-C 2F 5 7-C 2F 5 8-C 2F 5 6-Cl-7-OCHF 2 6-C 3F 7-i 6-C 3F 7-i 6-C 3F 7-i | m.p.98-102.4℃ nD 1.5660(22.8℃) m.p.168.7-171.9℃ nD 1.5400(21.1℃) m.p.139-146℃ m.p.198-201℃ m.p.96.1-101.3℃ nD 1.5163(23.3℃) nD 1.5211(23.3℃) |
Table 4 (continuing)
| No | R | R 1 | Xn | Physical properties |
| 487 488 489 490 491 492 493 494 495 496 497 498 499 500 501 | CH 2CN CH 2(3-Cl-Ph) COCH 2Br COCH 2OCH 3 CO(3-Cl-Ph) COOC 2H 5 COOC 4H 9-t COOCH 3 H COC 2H 5 H COCH 3 COC 2H 5 H H | Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 Q 2 | 6-C 3F 7-i 6-C 3F 7-i 6-C 3F 7-i 6-C 3F 7-i 6-C 3F 7-i 6-C 3F 7-i 6-C 3F 7-i 6-C 3F 7-i 6-OCH(CF 3) 2 6-OCH(CF 3) 2 6-CF 2CHFOCF 2 6-CF 2CHFOCF 2 6-CF 2CHFOCF 2 6-O-(3-CF 3-Ph) 6-O-(3-Cl-5- CF 3-2-Pyr) | m.p.109-113.1℃ nD 1.5329(20.6℃) nD 1.4910(23.5℃) nD 1.5106(21.6℃) m.p.54-58℃ m.p.140-148.3℃ nD 1.5598(23.4℃) m.p.130-135℃ m.p.137.5-139.9℃ nD 1.4932(23.4℃) m.p.119.8-119.9℃ nD 1.4977(21.3℃) nD 1.5000(24.4℃) m.p.113.8-116.0℃ m.p.75-81℃ |
Embodiment
Exemplary embodiments of the present invention is as described below, but these embodiment are not limited to scope of the present invention.
Embodiment 1
Preparation 3-amino-3,4-dihydro-6-trifluoromethoxy-2-(1H)-quinazolinone (compound N o.II-30)
2.84 gram (0.01 mole) 2-chloromethyl-4-Trifluoromethoxyphen-l Urethylanes are dissolved in 20 ml methanol, add 5 gram (0.1 mole) hydrazine hydrates then in this solution, reflux 3 hours is finished reaction.
After reaction is finished, remove residual hydrazine hydrate and solvent in the reaction mixture that contains the purpose compound by underpressure distillation, obtain crude product.With gained crude product 95% recrystallizing methanol, obtain 2.22 gram purpose compounds.
Physical properties: m.p.181.5-184 ℃.
Productive rate: 90%.
Embodiment 2
Preparation 3-amino-3,4-dihydro-6-pentafluoroethyl group-2-(1H)-quinazolinone (compound N o.II-18)
3.18 gram (0.01 mole) 2-chloromethyl-4-pentafluoroethyl group phenylcarbamic acid methyl esters are dissolved in 20 ml methanol, add 5 gram (0.1 mole) hydrazine hydrates then in this solution, reflux 3 hours is finished reaction.
After reaction is finished, remove residual hydrazine hydrate and solvent in the reaction mixture that contains the purpose compound by underpressure distillation, obtain crude product.With gained crude product 95% recrystallizing methanol, obtain 2.53 gram purpose compounds.
Physical properties: m.p.178.4-183.5 ℃.
Productive rate: 90%.
Embodiment 3
Preparation 3-(3-pyridyl methene amido)-3,4-dihydro-6-trifluoromethoxy-2-(1H)-quinazolinone (compound N is o.30)
With 0.62 gram (2.5 mmole) 3-amino-3,4-dihydro-6-trifluoromethoxy-2 (1H)-quinazolinone, 0.27 gram (2.5 mmole) nicotine aldehyde and 1 sulfuric acid add 10 ml methanol, and reflux 3 hours is finished reaction.
After reaction is finished, filter and collect the crystallization that is settled out in the reactive system, drying obtains 0.76 gram purpose compound.
Physical properties: m.p.264.5-266.0 ℃.
Productive rate: 93%.
Embodiment 4
Preparation 3-[1-(3-pyridyl methene amido)-3,4-dihydro-6-pentafluoroethyl group-2-(1H)-quinazolinone (compound N is o.18)
With 0.74 gram (2.5 mmole) 3-amino-3,4-dihydro-6-pentafluoroethyl group-2 (1H)-quinazolinone, 0.27 gram (2.5 mmole) nicotine aldehyde and 1 sulfuric acid add 10 ml methanol, and reflux 3 hours is finished reaction.
After reaction is finished, filter and collect the crystallization that is settled out in the reactive system, drying obtains 0.78 gram purpose compound.
Physical properties: m.p.298.0-300.0 ℃.
Productive rate: 84%.
Embodiment 5
Preparation 3-(3-pyridylmethyl amino)-3,4-dihydro-6-trifluoromethoxy-2-(1H)-quinazolinone (compound N is o.208)
With 3.36 gram (2.5 mmole) 3-(3-pyridyl methene amido)-3,4-dihydro-6-trifluoromethoxy-2-(1H)-quinazolinone and 0.2 gram, 5% palladium-carbon add 30 milliliters of acetate, then in 3 to 4 kilograms per centimeter
2Following hydrogenation.
After having absorbed theoretical amount hydrogen, by removing by filter the catalyzer in the reaction mixture, and underpressure distillation removes and desolvates.Add 20% aqueous sodium hydroxide solution neutralization residue, with chloroform (20 milliliters * 3) extraction purpose compound.With extraction liquid water and saturated aqueous sodium chloride washing, use anhydrous magnesium sulfate drying, and underpressure distillation is except that desolvating.The gained crude product by silica gel column chromatography (ethyl acetate-methyl alcohol=10: 1) purifying, is obtained 2.5 gram purpose compounds.
Physical properties: nD1.5233 (22.6 ℃).
Productive rate: 74%.
Embodiment 6
Preparation 1-methyl-3-(3-pyridylmethyl amino)-3,4-dihydro-6-trifluoromethoxy-2-(1H)-quinazolinone (compound N is o.289)
With 0.68 gram (2.0 mmole) 3-(3-pyridylmethyl amino)-3,4-dihydro-6-trifluoromethoxy-2-(1H)-quinazolinone is dissolved in 10 milliliters of dimethyl formamides.In this solution, add 0.09 gram sodium hydride (62.4%), and this reaction was at room temperature carried out 30 minutes, add 0.34 gram methyl iodide then, and reacted 4 hours.
After reaction is finished, reaction mixture is poured in the frozen water, with ethyl acetate (20 milliliters * 3) extraction purpose compound.With extraction liquid water and saturated aqueous sodium chloride washing, use anhydrous magnesium sulfate drying, and underpressure distillation is except that desolvating.The gained crude product by silica gel column chromatography (ethyl acetate-methyl alcohol=10: 1) purifying, is obtained 2.5 gram purpose compounds.
Physical properties: nD1.5467 (23 ℃).
Productive rate: 50%.
Embodiment 7
7-1. preparation 2-(5-hydroxyl-2-nitrophenyl methylene radical) tert-butyl carbazate
With 3.34 gram (0.02 mole) 5-hydroxyl-2-nitrobenzaldehydes, 2.64 gram (0.02 mole) tert-butyl carbazates and 1 sulfuric acid add 20 ml methanol, and reflux 3 hours is finished reaction.
After reaction is finished, reaction mixture is cooled to room temperature, filters the crystallization that collecting precipitation goes out, obtain 5.06 gram purpose compounds.
1H-NMR[CDCl
3/TMS，δ(ppm)]
1.57(9H，s)，6.84(1H，d.d)，7.66(1H，d)，
7.94(1H，d)，8.42(1H，br.s)，8.46(1H，s)，
10.5(1H，br.s).
Productive rate: 90%.
7-2. preparation 2-(5-methoxycarbonyl oxygen base-2-nitrophenyl methylene radical) tert-butyl carbazate
2-(5-hydroxyl-2-nitrophenyl methylene radical) tert-butyl carbazate and 1.67 gram (0.0165 mole) triethylamines that 4.22 gram (0.015 mole) embodiment 7-1 are obtained are dissolved in 15 milliliters of tetrahydrofuran (THF)s, are cooled to 0 ℃ then.Place after 15 minutes, in this solution, drip 1.56 gram (0.0165 mole) methyl-chloroformates that are dissolved in 5 milliliters of tetrahydrofuran (THF)s, this reaction was at room temperature carried out 3 hours.After reaction is finished, reaction mixture to going in 20 ml waters, is extracted the purpose compound with ethyl acetate (20 milliliters * 3).With extraction liquid water and saturated aqueous sodium chloride washing, use anhydrous magnesium sulfate drying, and underpressure distillation with hexane-ether recrystallization purifying, obtains 4.6 gram purpose compounds with the gained crude product except that desolvating.
1H-NMR[(CDCl
3/TMS，δ(ppm)]
1.54(9H，s)，3.93(3H，s)，7.33(1H，d.d)，
8.06(1H，d)，8.14(1H，d)，8.21(1H，br.s)，
8.45(1H，s).
Productive rate: 90%.
7-3. preparation 2-(2-amino-5-methoxycarbonyl oxygen base phenyl methyl) tert-butyl carbazate
2-(5-methoxycarbonyl oxygen base-2-nitrophenyl methylene radical) tert-butyl carbazate and 0.4 gram 5% palladium-carbon that 4.4 gram (0.013 mole) embodiment 7-2 are obtained add 50 ml methanol, then in 3 to 4 kilograms per centimeter
2Following catalytic reduction.
After having absorbed theoretical amount hydrogen, by removing by filter the catalyzer in the reaction mixture, and underpressure distillation removes and desolvates, and obtains 4 gram purpose compounds.
1H-NMR[(CDCl
3/TMS，δ(ppm)]
1.46(9H，s)，3.87(3H，s)，3.96(2H，d)，
4.6-5.0(3H，br.s.)，6.05(1H，br.s)，
6.6-6.7(1H，m)，6.8-7.0(2H，m).
Productive rate: quantitatively.
7-4. preparation 3-t-butoxycarbonyl amino-6-methoxycarbonyl oxygen base-3,4-dihydro-2 (1H)-quinazolinone
2-(2-amino-5-methoxycarbonyl oxygen base phenyl methyl) tert-butyl carbazate and 2.6 that 3.1 gram (0.01 mole) embodiment 7-3 are obtained restrains (0.01 moles) 1,1 '-carbonyl-two (1H-imidazoles) is dissolved in 20 milliliters of tetrahydrofuran (THF)s, and this reaction was at room temperature carried out 3 hours.
After reaction is finished, reaction mixture to going in 20 ml waters, is extracted the purpose compound with ethyl acetate (20 milliliters * 3).With extraction liquid water and saturated aqueous sodium chloride washing, use anhydrous magnesium sulfate drying, and underpressure distillation is except that desolvating.The gained crude product with hexane-re-crystallizing in ethyl acetate purifying, is obtained 2.1 gram purpose compounds.
1H-NMR[DMSO-d
6/TMS，δ(ppm)]
1.42(9H，s)，3.80(3H，s)，4.81(2H，s)，6.5-6.7(3H，m)，9.01(1H，s)，9.15(1H，br.s).
Productive rate: 60%.
7-5. preparation 3-t-butoxycarbonyl amino-6-hydroxyl-3,4-dihydro-2 (1H)-quinazolinone
Restrain 3-t-butoxycarbonyl amino-6-methoxycarbonyl oxygen base-3 that (0.0062 mole) embodiment 7-4 obtain with 2.1,4-dihydro-2 (1H)-quinazolinone and 0.64 gram (0.0063 mole) yellow soda ash are dissolved in 20 milliliter of 50% methyl alcohol, this is reflected at carried out under the reflux 3 hours.
After reaction was finished, methyl alcohol was removed in underpressure distillation.The gained residue is added in 10 ml waters, and filter and collect, use 95% recrystallizing methanol purifying then, obtain 1.3 gram purpose compounds.
1H-NMR[DMSO-d
6/TMS，δ(ppm)]
1.42(9H，s)，4.81(2H，s)，6.5-6.7(3H，s)，9.01(1H，s)，9.10(1H，s)，9.15(1H，br.s).
Productive rate: 75%.
7-6. preparation 3-amino-6-hydroxyl-3,4-dihydro-2 (1H)-quinazolinone (compound N o.II-2)
With 3-t-butoxycarbonyl amino-6-hydroxyl-3 that 1.3 gram (0.0046 mole) embodiment 7-5 obtain, 4-dihydro-2 (1H)-quinazolinone adds 20 milliliters of trifluoroacetic acids, and this reaction was at room temperature carried out 3 hours.
After reaction is finished, 10 ml methanol are added reaction mixture, underpressure distillation removes and desolvates.With gained residue recrystallizing methanol, obtain 0.74 gram purpose compound.
1H-NMR[DMSO-d
6/TMS，δ(ppm)]
4.95(2H，s)，4.65(2H，s)，6.51-6.63(3H，m)，9.00(1H，s)，9.60(1H，br.s).
Productive rate: 90%.
Contain aminoquinazolinone (thioketones) derivative that general formula of the present invention (I) replaces or its salt and be applicable to various hexapeopoda pests of control such as agricultural insect insect as the agent for controlling noxious insect pests of effective constituent, the forest-insect insect, horticultural insect pest, cereal stores insect pest, the environmental health insect pest, nematode, etc.They also have insecticidal action to for example following insect, Hemiptera, comprise Empoasca onukii (green tea leafhopper), Nephotettix cincticeps (rice green leafhopper), Nilaparvata lugens (Nilaparvata lugen (brown planthopper)), Sogatella furcifera (carrying on the back the rice lice in vain), Diaphorina citri (tangerine wood louse), Dialeurodescitri (whitefly), Bemisia tabaci (sweet potato whitefly), Trialeurodesvaporariorum (trialeurodes vaporariorum), Brevicoryne brassicae (brevicoryne brassicae), Aphisgossypii (cotten aphid), Rhopalosiphum padi (rhopalosiphum padi), Myzus persicae (black peach aphid), Ceroplastes ceriferus (ceroplastes), Pulvinaria aurantii (yellowish green wadding a red-spotted lizard), Pseudaonidia duplex (snake eye a red-spotted lizard), Comstockaspis perniciosa (San Jose scale), Unaspis yanonensis (arrowhead scales), Trigonotylus colelestialium, Deng, Tylenchida comprises Pratylenchus coffeae (coffee dissociate root nematode), Globoderarostochiensis (potato Cyst nematode), Meloidogyne sp. (root nodule nematode), Tylenchulus semipenetrans (oranges and tangerines nematode), Aphelenchus avenae (Aphelenchus avenae), Aphelenchoides ritzemabosi (chrysanthemum leaf aphelenchoides), Deng, Orthoptera comprises Stenchaetothrips biformis, etc.
The foundation of the title of experimental animal is " the List of Agricultural and Forest Injurious Animals and Insects " that Japanese applied zoology and insectology association published in 1987.
Contain aminoquinazolinone (thioketones) derivative that general formula of the present invention (I) replaces or its salt the hexapeopoda pest of agent for controlling noxious insect pests to above enumerating as effective constituent, public health insect, and/or nematode has the obvious suppression effect, these insects are to the rice field, fruit tree, vegetables and other crops, and flowers and decorative plant are harmful.Therefore, by in paddy field water either, paddy rice, fruit tree, vegetables, other crops, the seed of flowers and decorative plant, the root of plant, stem and leaf, earth, etc., or the inside, house or the irrigation canals and ditches around the house that occur maybe may occurring people and the deleterious above-mentioned environmental health insect pest of livestock use agent for controlling noxious insect pests of the present invention, can obtain gratifying insecticidal effect.Dispenser season is an insect pest, and public health insect and nematode may occur, before occurring or confirm season of occurring.Yet the present invention is not limited to these embodiments.
When aminoquinazolinone (thioketones) derivative that general formula of the present invention (I) replaces or its salt are used as agent for controlling noxious insect pests, should it be prepared into form easy to use by agricultural chemicals conventional formulation mode.
That is to say that the suitable inert support that aminoquinazolinone (thioketones) derivative that general formula of the present invention (I) replaces or its salt and the auxiliary that exists arbitrarily and ratio are suitable is mixed together; By dissolving, disperse, suspend, mix, to soak into, absorption or bonding is prepared into the appropriate formulations form, as suspension agent, missible oil, solubilized enriching agent, wettable powder, granule, pulvis or tablet.
The used inert support of the present invention both can be solid, also can be liquid.The example of solid carrier is a bean powder, flour, wood powder, tree bark powder, sawdust, powdered tobacco stalk, the powdery nut-shell, rice bran, Solka-floc, the plant extraction residue, powdery synthetic polymer or resin, clay are (for example, kaolin, wilkinite, and acid clay), talcum (for example talcum and pyrophyllite), ground silica or silica sheet (diatomite, silicon sand, mica and white carbon, promptly the silicic acid of synthetic high dispersive is also referred to as finely powdered hydration silica or silicate hydrate, the contained main component of some commercially available product is a Calucium Silicate powder), gac, sulphur powder, the powdery float stone, roasting diatomite, brickbat, floating dust, sand, powder lime carbonate, powdered acid calcium and other inorganic or mineral dusts, chemical fertilizer (ammonium sulfate for example, ammonium phosphate, ammonium nitrate, urea and ammonium chloride), and compost.These carriers both can use separately, also can mix use.
Itself have solvability or do not have solvability but can be by the liquid of auxiliary dispersed activity composition although liquid vehicle is those.Be the exemplary of some liquid vehicles below, they both can use separately also can mix use.Water; Alcohols such as methyl alcohol, ethanol, Virahol, butanols and ethylene glycol; Ketone such as acetone, methylethylketone, mibk, diisobutyl ketone and pimelinketone; Ethers such as ether, two alkane, cellosolve, dipropyl ether and tetrahydrofuran (THF); Aliphatic hydrocrbon such as kerosene and mineral oil; Aromatic hydrocarbon such as benzene, toluene, dimethylbenzene, solvent naphtha and alkylnaphthalene; Halohydrocarbon such as ethylene dichloride, chloroform and tetracol phenixin; Ester class such as ethyl acetate, phthalic acid diisopropyl ester, dibutyl phthalate and phthalic acid dioctyl ester; Amides such as dimethyl formamide, diethylformamide and N,N-DIMETHYLACETAMIDE; Nitrile such as acetonitrile; And methyl-sulphoxide.
Be the exemplary of auxiliary below.Purposes is depended in the use of auxiliary, needs sometimes to use separately, need merge use sometimes, does not then need sometimes to use.
For emulsification, to disperse, dissolving and/or wetting active ingredient can be used tensio-active agent.The example of tensio-active agent is a Voranol EP 2001, polyoxyethylene alkylaryl ether, the polyoxyethylene high-grade aliphatic ester, the polyoxyethylene resinate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monooleate, alkyl aryl sulfonate, naphthalene sulfonic acid condensate, lignosulfonic acid ester and higher alcohol sulfate.
In addition,, make its tackify and/or combination, can use auxiliary for the stabilizing active component disperser, as casein, gelatin, starch, methylcellulose gum, carboxymethyl cellulose, gum arabic, polyvinyl alcohol, turps, oil extracted from rice husks, wilkinite and Sulfite lignin.
In order to improve the flowability of solid product, can use auxiliary, as paraffin, stearate and alkyl phosphate.
Auxiliary such as naphthalene sulfonic acid condensate and phosphoric acid ester polycondensate also can be used as the peptizing agent that can disperse product.
Auxiliary such as silicone oil can be used as defoamer.
The concentration of active ingredient can change as required.In pulvis or granule, suitable concentration is 0.01 to 50% (weight).In missible oil maybe can flow moistening powder, suitable concentration also was 0.01 to 50% (weight).
Aminoquinazolinone (thioketones) derivative or its salt that contain general formula of the present invention (I) replacement can be controlled various insect pests in the following manner as the agent for controlling noxious insect pests of effective constituent.That is, with control insect pest effective concentration, with said preparation, or with said preparation in water or other thinners suitably dilution or suspend after, be applied to insect pest, or do not wish to occur or the place of the insect pest of growing.
Contain aminoquinazolinone (thioketones) derivative that general formula of the present invention (I) replaces or its salt and depend on various factors as the dosage of the agent for controlling noxious insect pests of effective constituent, as purpose, the kind of controlled insect, the upgrowth situation of plant, the trend that insect pest occurs, weather, environmental aspect, formulation, application method, dispenser place and spraying time.According to the difference of purpose, suitable dosage ranges is per 10 are 0.1 and restrains 5 kilograms (in active ingredients).
In order to enlarge the scope of may command insect pest, prolong spraying cycle or reduce dispenser dosage, contain aminoquinazolinone (thioketones) derivative that general formula of the present invention (I) replaces or its salt and can mix use with other agent for controlling noxious insect pests or mycocide as the agent for controlling noxious insect pests of effective constituent.
Hereinafter will describe typical formulation embodiment of the present invention and experimental example, but can not limit the scope of the invention with it.
In example of formulations, umber all by weight.
Example of formulations 1
50 parts of table 3 and 4 listed each compounds
40 parts of dimethylbenzene
10 parts in the mixture of polyoxyethylene nonylplenyl ether and alkyl benzene calcium sulfonate
Make its dissolving obtain missible oil by the uniform mixing said components.
Example of formulations 2
3 parts of table 3 and 4 listed each compounds
82 parts of clay powders
15 parts of diatomites in powder
By with said components uniform mixing and grinding, obtain pulvis.
Example of formulations 3
5 parts of table 3 and 4 listed each compounds
90 parts of the mixed powders of wilkinite and clay
5 parts of calcium lignosulfonates
By with the said components uniform mixing, with suitable quantity of water the gained mixture is mediated, granulate and drying, obtain granule.
Example of formulations 4
20 parts of table 3 and 4 listed each compounds
75 parts in the mixture of kaolin and synthetic high dispersive silicic acid
5 parts in the mixture of polyoxyethylene nonylplenyl ether and alkyl benzene calcium sulfonate
By with said components uniform mixing and grinding, obtain wettable powder.
Experimental example 1
Prevention effect to Myzus persicae (black peach aphid)
Plantula Brassicae chinensis is planted in 8 centimetres of diameters and high 8 centimetres each plastic tub, black peach aphid is propagated on Plantula Brassicae chinensis, count the parasite in each basin then.
Aminoquinazolinone (thioketones) derivative or its salt that the general formula various of the present invention (I) that table 3 and 4 is enumerated replaces are dispersed in the water, and dilute with water, obtain the liquid preparation of 500ppm.Spray the aforesaid liquid preparation on stem of Plantula Brassicae chinensis in basin and the leaf and, be placed in the greenhouse then at air drying.The spray medicine is after six days, and record colonizes in the black peach aphid number on each Plantula Brassicae chinensis, presses following equation and calculates prevention effect, presses hereinafter described standard then and judges insecticidal effect.
Prevention effect=100-{ (T * Ca)/(Ta * C) } * 100
Ta: number of parasites before the treatment group spray medicine,
T: number of parasites behind the treatment group spray medicine,
Ca: number of parasites before the untreated fish group spray medicine,
C: number of parasites behind the untreated fish group spray medicine.
Judging criterion:
Effect control percentage ratio (%)
A 100
B 99-90
C 89-80
D 79-50
Experimental example 2
Insecticidal effect to Nilaparvata lugens (Nilaparvata lugen (brown planthopper))
Aminoquinazolinone (thioketones) derivative or its salt that the general formula various of the present invention (I) that table 3 and 4 is enumerated replaces are dispersed in the water, and dilute with water, obtain the liquid preparation of 500ppm.With rice seedling (kind: Nihonbare) in medicament, soaked 30 seconds and, then each rice shoot placed glass test tube at air drying, and in each test tube inoculation rice brown planthopper nymph in 10 three ages, test tube is clogged with cotton plug.Inoculate after eight days record worm alive and dead borer population amount.Press following equation and calculate mortality ratio, press hereinafter described standard then and judge the control effect.
Gauged larval mortality (%)=100-{ (Ca/C-Ta/T)/Ca/C} * 100
Ta: treatment group nymph number alive,
T: treatment group inoculation nymph number,
Ca: untreated fish group nymph number alive,
C: untreated fish group inoculation nymph number.
Judging criterion: identical with experimental example 1.
Experimental example 3
Insecticidal effect to Trialeurodes vaporariorum (greenhouse whitefly)
Aminoquinazolinone (thioketones) derivative or its salt that table 3 and 4 every kinds of enumerating general formula of the present invention (I) are replaced are dispersed in the water, and dilute with water, obtain the liquid preparation of 100ppm.Use atomizer that test medicine is sprayed at the tomato leaf surface, this tomato leaf places the moisture 20ml bottle on the turntable.To be placed on the tomato leaf that test medicine was handled in the glass infuser after the dry air, inoculate 20 greenhouse whitefly adults.Then, this tomato leaf is placed the greenhouse, the quantity of record trialeurodes vaporariorum adult.By calculating the mortality ratio of adult, judge the insecticidal effect of each test compound by the method identical with experimental example 1 with experimental example 2 similar methods.
The result who obtains from experimental example 1,2 and 3 is as follows: in the experimental example 1, be numbered 6,18,22,26,30,184,200,204 and 208 compound is shown as the A level to Myzus persicae (black peach aphid) outstanding insecticidal effect; In the experimental example 2, be numbered 6,18,22,26,30,184,200,204 and 208 compound is shown as the A level to Nilaparvata 1ugens (Nilaparvata lugen (brown planthopper)) outstanding insecticidal effect; And in the experimental example 3, being numbered 6,10,14,18,22,26,30,38,78,86,90,184,200,204 and 208 compound is shown as D level or the outstanding insecticidal effect of high-grade more to Trialeurodesvaporariorum (greenhouse whitefly); Particularly, be numbered the outstanding insecticidal effect that 6,18,22,26,30,184,200,204 and 208 compound exhibits goes out the A level.
Claims (4)
1. the amido quinazoline ketone derivatives of the replacement of general formula (I) expression, or its salt:
Wherein R is the methyl carbonyl, R
1Be the 3-pyridyl, Y is a Sauerstoffatom, and Z is-N=C (R
2)-
R wherein
2Be hydrogen atom, X is i-C
3F
7, n is 1.
2. according to amido quinazoline ketone derivatives or its salt of the replacement of claim 1, it is a following formula: compound
3. contain the amido quinazoline ketone derivatives of replacement of claim 1 or 2 or its salt agent for controlling noxious insect pests as active ingredient.
4. the method for a pest control is applied to target crop or soil comprising the amido quinazoline ketone derivatives that will contain the replacement in claim 1 or 2 or its salt as the agent for controlling noxious insect pests of active ingredient.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31229799 | 1999-11-02 | ||
| JP312297/1999 | 1999-11-02 | ||
| JP094493/2000 | 2000-03-30 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN001368583A Division CN1302801B (en) | 1999-11-02 | 2000-11-02 | Substituted aminoquinazolone (thio-ketone) derivative or its salt, its intermediate and pest controlling agent and its application method |
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|---|---|
| CN101239973A true CN101239973A (en) | 2008-08-13 |
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| CNA2008100837010A Pending CN101239973A (en) | 1999-11-02 | 2000-11-02 | Substituted aminoquinazolinone (thione) derivative or salts thereof, intermediate compound therefor, pest-controlling agent and using method thereof |
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| CN104904742A (en) * | 2014-03-11 | 2015-09-16 | 江苏龙灯化学有限公司 | Insect disinfestation composition and pest control method |
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- 2000-11-02 CN CNA2008100837010A patent/CN101239973A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104904742A (en) * | 2014-03-11 | 2015-09-16 | 江苏龙灯化学有限公司 | Insect disinfestation composition and pest control method |
| WO2015135420A1 (en) * | 2014-03-11 | 2015-09-17 | 江苏龙灯化学有限公司 | Pesticidal composition and method for controlling pests |
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