TREA

Fungicidal N-phenylcarbamates

Follow

Information

  • Patent Grant
  • 4690946
  • Patent Number
    4,690,946
  • Date Filed
    Friday, October 14, 1983
    41 years ago
  • Date Issued
    Tuesday, September 1, 1987
    37 years ago
Information
Abstract
Use of an N-phenylcarbamate of the formula: ##STR1## as a fungicidal agent against phytopathogenic fungi, particularly strains which are resistant to benzimidazole thiophanate fungicides and/or cyclic imide fungicides.
Description

This invention relates to fungicidal N-phenyl-carbamates.
Benzimidazole and thiophanate fungicides such as Benomyl (methyl 1-(butylcarbamoyl)benzimidazol-2-ylcarbamate), Fubelidazol (2-(2-furyl)benzimidazole), Thiabendazole (2-(4-thiazolyl)benzimidazole), Carbendazim (methyl benzimidazol-2-ylcarbamate), Thiophanate-methyl (1,2-bis(3-methoxycarbonyl-2-thioureido)benzene), Thiophanate (1,2-bis(3-ethoxycarbonyl-2-thioureido)benzene), 2-(O,S-dimethylphosphorylamino)-1-(3'-methoxycarbonyl-2'-thioureido)benzene and 2-(O,O-dimethylthiophosphorylamino)-1-(3'-methoxycarbonyl-2'-thioureido)benzene are known to show an excellent fungicidal activity against various plant pathogenic fungi, and they have been widely used as agricultural fungicides since 1970. However, their continuous application over a long period of time results in phytopathogenic fungi becoming tolerant to the fungicides, whereby their plant disease-preventive effect is much lowered. Further, the fungi which gain tolerance to certain kinds of benzimidazole or thiophanate fungicides also show considerable tolerance to some other kinds of benzimidazole or thiophanate fungicides. Thus, they are apt to obtain crosstolerance. Therefore, if any material decrease of their plant disease-preventive effect in certain fields is observed, their application to such fields has to be discontinued. But, it is often observed that the density of drug-resistant organisms is not decreased even long after the discontinuation of the application. Although other kinds of fungicides have to be employed in such a case, only few are as effective as benzimidazole or thiophanate fungicides in controlling various phytopathogenic fungi. Benzimidazole and thiophanate fungicides are hereinafter referred to as "benzimidzole and thiophanate fungicides". Cyclic imide fungicides such as Procymidone (3-(3',5'-dichlorophenyl)-1,2-dimethylcyclopropane-1,2-dicarboximide), Iprodione (3-(3',5'-dichlorophenyl)-1-isopropylcarbamoylimidazolidine-2,4-dione), Vinchlozolin (3-(3',5'-(dichlorophenyl)-5-methyl-5-vinyloxazolidine-2,4-dione), ethyl (RS)-3-(3',5'-dichlorophenyl)-5-methyl-2,4-dioxooxazolidine-5-carboxylate, etc., which are effective against various plant diseases, particularly those caused by Botrytis cinerea, have the same defects as previously explained with respect to the benzimidazole thiophanate fungicides.
In C.R. Acad. Sc. Paris, t. 289, S'erie D, pages 691-693 (1979), it is described that herbicides such as Barban (4-chloro-2-butynyl N-(3-chlorophenyl)carbamate), Chlorobufam (1-methyl-2-propynyl N-(3-chlorophenyl)carbamate), Chlorpropham (isopropyl N-(3-chlorophenyl)carbamate) and Propham (isopropyl N-phenylcarbamate) exhibit a fungicidal activity against certain organisms tolerant to some of the benzimidazole thiophanate fungicides. However, their fungicidal activity against the drug-resistant fungi is not strong enough, and hence, practically they can not be used as fungicides.
As a result of the study seeking a new type of fungicides, it has now been found that N-phenylcarbamates of the formula: ##STR2## wherein X and Y, which may be the same or different, are each a halogen atom, a lower alkyl group, a lower alkenyl group, a lower cyanoalkenyl group, a lower alkynyl group, a lower alkoxy group, a cyano group, a lower alkyl group substituted with at least one member selected from the group consisting of halogen, hydroxyl and cyano, or a group of the formula: ##STR3## in which R.sup.3 is a lower alkyl group, a lower alkenyl group, a lower alkynyl group or a lower haloalkyl group, R.sup.4 and R.sup.5, which may be the same or different, are each a lower alkyl group, R.sup.6 is a hydrogen atom or a lower alkyl group, n is 2, 3 or 4; Z is an oxygen atom or a sulfur atom; R.sup.1 a lower alkyl group, a lower alkenyl gruop, a lower alkynyl group or a lower alkyl group substituted with at least one member selected from the group consisting of halogen, lower alkoxy and lower cycloalkyl and R.sup.2 is a C.sub.1 -C.sub.8 alkyl group, a C.sub.3 -C.sub.8 alkenyl group, a lower cycloalkyl group, a lower haloalkenyl group, a lower haloalkynyl group or a lower alkyl group substituted with at least one member selected from the group consisting of halogen, cyano, lower alkoxy, lower alkenyloxy, lower haloalkoxy, phenoxy, lower aralkyloxy and lower cycloalkyl, show an excellent fungicidal activity against plant pathogenic fungi which have developed resistance to benzimidazole thiophanate fungicides and/or cyclic imide fungicides. It is notable that their fungicidal potency against the organisms tolerant to benzimidazole thiophanate fungicides and/or cyclic imide fungicides (hereinafter referred to as "drug-resistant fungi" or "drug-resistant strains") is much higher than that against the organisms sensitive to benzimidazole thiophanate fungicides and/or cyclic imide fungicides (hereinafter referred to as "drug-sensitive fungi" or "drug-sensitive strains").
All the N-phenylcarbamates (I) are novel compounds except ethyl N-(3,4,5-trimethoxyphenyl)carbamate, ethyl N-(3,4,5-triethoxyphenyl)carbamate, propargyl N-(4-methoxy-3,5-dibromophenyl)carbamate, methyl N-(4-methoxy-3,5-dichlorophenyl)thiolcarbamate, methyl N-(3-bromo-4-methoxy-5-chlorophenyl)thiolcarbamate and 2-butynyl N-(3,4,5-trimethoxyphenyl)carbamate are known. These compounds have been known, but it has not been known or reported that they have fungicidal activity or that they are useful as fungicides [DT-OS No. 2,041,986, French patent M8200, Arch. Pharm., 272, 221-235 (1934)].
Thus, the present invention provides a fungicidal composition which comprises, as an active ingredient, a fungicidally effective amount of the N-phenylcarbamate (I) and an inert carrier or diluent. It also provides a combination composition comprising as active ingredients the N-phenylcarbamate (I) together with a benzimidazole thiophanate fungicide and/or a cyclic imide fungicide, which is fungicidally effective against not only drug-sensitive fungi but also drug-resistant fungi, and hence particularly effective for the prevention of plant diseases. It also provides a method of controlling plant pathogenic fungi including drug-resistant strains and drug-sensitive strains applying a fungicidally effective amount of the N-phenyl-carbamate (I) to plant pathogenic fungi. It further provides novel N-phenylcarbamates which are representable by the formula (I) wherein X, Y, Z, R.sup.1 and R.sup.2 are each as defined above. It furthermore provides a process for producing the novel N-phenylcarbamates (I), which comprises reacting a 3,4,5-trisubstituted aniline of the formula: ##STR4## wherein X, Y and R.sup.1 are each as defined above, with a chloroformate of the formula: ##STR5## wherein Z and R.sup.2 are each as defined above (Procedure (a)), or reacting a 3,4,5-trisubstituted phenyl isocyanate of the formula: ##STR6## wherein X, Y and R.sup.1 are each as defined above, with an alcohol or thiol of the formula:
HZR.sup.2 (V)
wherein Z and R.sup.2 are each as defined above (Procedure (b)). Moreover, it provides a process for producing the N-phenylcarbamates of the formula (I) wherein at least one of X and Y is a hydroxyiminomethyl group or a lower alkoxyiminomethyl group, which comprises reacting a benzaldehyde of the formula: ##STR7## wherein Y, Z, R.sup.1 and R.sup.2 are each as defined above, with hydroxyamine or lower alkoxyamine (Procedure (c)).
The term "lower" used hereinabove and hereinafter in connection with organic radicals or compounds indicates that such radicals or compounds each have not more than 6 carbon atoms. Preferable X and Y are fluorine, chlorine, bromine, iodine, methyl, ethyl, n-propyl, n-butyl, vinyl, 1-propenyl, 2-propenyl, ethynyl, methoxy, ethoxy, cyano, 1,2-dibromoethyl, hydroxymethyl, cyanomethyl, 2-cyanoethyl, 2-cyanovinyl, methoxymethyl, ethoxymehyl, allyloxymethyl, propargyloxymethyl, 2-fluoroethoxymethyl, methoxycarbonyl, ethoxycarbonyl, allyloxycarbonyl, 2-fluoroethoxycarbonyl, propargyloxycarbonyl, dimethoxymethyl, idethoxymethyl, ethylenedioxymethyl, formyl, acetyl, hydroxyiminomethyl, methoxyiminomethyl, carbamoyl or N-methylcarbamoyl. Particularly preferred X and Y are fluorine, chlorine, bromine, iodine, methyl, ethyl, n-propyl, vinyl, 1-propenyl, 2-propenyl, ethynyl, methoxy, ethoxy, cyano, 1,2-dibromoethyl, methoxymethyl, methoxycarbonyl, dimethoxymethyl, diethoxymethyl, acetyl or methoxyiminomethyl. Especially active are those compounds wherein X and Y are each fluorine, chlorine, bromine, methoxymethyl, methyl, ethyl or n-propyl, and those compounds wherein X is fluorine, chlorine, bromine, methoxy or ethoxy and Y is chlorine, bromine, methyl, ethyl, n-propyl, methoxy, ethoxy, cyano, methoxymethyl, methoxycarbonyl, dimethoxymethyl or acetyl. Preferred Z is oxygen. Preferable R.sup.1 is methyl, ethyl, n-propyl, allyl, 2-butenyl, 3-butenyl, propargyl, 3-butynyl, difluoromethyl, 2-chloroethyl, 2-fluoroethyl, 2,2,2-trifluoroethyl, 2-methoxyethyl or cyclopropylmethyl. Particularly preferable R.sup.1 is methyl, ethyl, allyl, propargyl, difluoromethyl, 2-fluoroethyl, 2,2,2-trifluoroethyl or 2-chloroethyl. Most preferable R.sup.1 is ethyl, allyl, propargyl, 2-fluoroethyl, 2,2,2-trifluoroethyl or 2-chloroethyl. Preferable R.sup.2 is methyl, ethyl, isopropyl, sec-butyl, allyl, 1-ethylpropyl, 1-methylbutyl, 1-methylpentyl, 1-methylheptyl, 1-methyl-2-propenyl, propargyl, 2-butenyl, 1-methyl-3-butenyl, 1-pentyl-2-propenyl, 1-methyl-2-propynyl, 1-ethyl-2-propynyl, 2-butynyl, 3-butynyl, 1-methyl-3-butynyl, 1-butyl-2-propynyl, 1-pentyl-2-propynyl, cyclobutyl, 2-cyanoethyl, 2fluoroethyl, 2-chloroethyl, 2-bromoethyl, 2,2,2-trifluoroethyl, 1-fluoromethyl-2-fluoroethyl, 1-chloromethylethyl, 1-bromomethylpropyl, 1-methoxymethyl-2-chloroethyl, 4-chloro-2-butenyl, 4-chloro-2 -butynyl, 1-cyclopropylethyl, 1-cyclopentylethyl, 2-methoxyethyl, 2-n-propoxyethyl, 2-isopropoxyethyl, 2-allyloxyethyl, 2-(2-chloroethoxy)ethyl, 2-benzyloxyethyl, 1-methyl-2-methoxyethyl, 1-methyl-2-n-butoxyethyl or 1-methyl-2-phenoxyethyl. Particularly preferable R.sup.2 is methyl, ethyl, isopropyl, sec-butyl, 1-ethylpropyl, allyl, 1-methyl-2-propenyl, 2-butenyl, propargyl, 1-methyl-2-propynyl, 1-ethyl-2-propynyl, 2-butynyl, 1-methyl-3-butynyl, 2-cyanoethyl, 2-fluoroethyl, 1-fluoromethyl-2-fluoroethyl, 1-chloromethylethyl, 1-methoxymethyl-2-chloroethyl, 4-chloro-2-butynyl, 1-cyclopropylethyl, 2-(2-chloroethoxy)-ethyl, 1-methyl-2-methoxyethyl or 1-methyl-2-n-butoxyethyl. Most preferable R.sup.2 is methyl, ethyl, isopropyl, sec-butyl, allyl, 1-methyl-2-propenyl, 1-methyl-2-propynyl, propargyl, 2-butynyl, 2-cyanoethyl, 4-chloro-2-butynyl or 1methyl-2-methoxyethyl.
The N-phenylcarbamates (I) are fungicidally effective against a wide scope of plant pathogenic fungi, of which examples are as follows: Podosphaera leucotricha, Venturia inaequalis, Mycosphaerella pomi, Marssonina mali and Sclerotinia mali of apple, Phyllactinia Kakicola and Gloeosporium kaki of persimmon, Cladosporium carpophilum and Phomopsis sp. of peach, Cercospora viticola, Uncinula necator, Elsinoe ampelina and Glomerella cingulata of grape, Cercospora beticola of sugarbeet, Cercospora arachidicola and Cercospora personata of peanut, Erysiphe graminis f. sp. hordei, Cercosporella herpotrichoides and Fusarium nivale of barley, Erysiphe graminis f. sp. tritici of wheat, Sphaerotheca fuliginea and Cladosporium cucumerinum of cucumber, Cladosporium fulvum of tomato, Corynespora melongenae of eggplant, Sphaerotheca humuli, Fusarium oxysporum f. sp. fragariae of strawberry, Botrytis alli of onion, Cercospora apii of cerely, Phaeoisariopsis griseola of kidney bean, Erysiphe cichoracearum of tobacco, Diplocarpon rosae of rose, Elsinoe fawcetti, Penicillium italicum, Penicillium digitatum of orange, Botrytis cinerea of cucumber, eggplant, tomato, strawberry, pimiento, onion, lettuce, grape, orange, cyclamen, rose or hop, Sclerotinia sclerotiorum of cucumber, eggplant, pimiento, lettuce, celery, kidney bean, soybean, azuki bean, potato or sunflower, Sclerotinia cinerea of peach or cherry, Mycosphaerella melonis of cucumber or melon, etc. Namely, the N-phenylcarbamates (I) are highly effective in contolling the drug-resistant strains of said fungi.
The N-phenylcarbamates (I) are also fungicidally effective against fungi sensitive to said known fungicides as well as fungi to which said known fungicides are ineffective. Examples of such fungi are Pyricularia oryzae, Pseudoperonospora cubensis, Plasmopara, viticola, Phytophthora infestans, etc.
Advantageously, the N-phenylcarbamates have low toxicity and have little detrimental action on mammals, fish and so on. Also, they may be applied to an agricultural field without causing any material toxicity to important crop plants.
In view of their excellent fungicidal properties, particularly useful are the compounds of the formula (I) wherein X and Y are independently fluorine, chlorine, bromine, iodine, methyl, ethyl, n-propyl, n-butyl, vinyl, 1-propenyl, 2-propenyl, ethynyl, methoxy, ethoxy, cyano, 1,2-dibromoethyl, hydroxymethyl, cyanomethyl, 2-cyanoethyl, 2-cyanovinyl, methoxymethyl, ethoxymethyl, allyloxymethyl, propargyloxymethyl, 2-fluoroethoxymethyl, methoxycarbonyl, ethoxycarbonyl, allyloxycarbonyl, 2-fluoroethoxycarbonyl, propargyloxycarbonyl, dimethoxymethyl, diethoxymethyl, ethylenedioxymethyl, formyl, acetyl, hydroxyiminomethyl, methoxyiminomethyl, carbamoyl or N-methylcarbamoyl, Z is oxygen or sulfur, R.sup.1 is methyl, ethyl, n-propyl, allyl, 2-butenyl, 3-butenyl, propargyl, 3-butynyl, difluoromethyl, 2-chloroethyl, 2-fluoroethyl, 2,2,2-trifloroethyl, 2-methoxyethyl or cyclopropylmethyl, R.sup.2 is methyl, ethyl, isopropyl, sec-butyl, allyl, 1-ethylpropyl, 1-methylbutyl, 1-methylpentyl, 1-methylheptyl, 1-methyl-2-propenyl, propargyl, 2-butenyl, 1-methyl-3-butenyl, 1-pentyl-2-propenyl, 1-methyl-2-propynyl, 1-ethyl-b 2-propynyl, 2-butynyl, 3-butynyl, 1-methyl-3-butynyl, 1-butyl-2-propynyl, 1-pentyl-2-propynyl, cyclobutyl, 2-cyanoethyl, 2-fluoroethyl, 2-chloroethyl, 2-bromoethyl, 2,2,2-trifluoroethyl, 1-fluoromethyl-2-fluoroethyl, 1-chloromethylethyl, 1-bromomethylpropyl, 1-methoxymethyl-2-chloroethyl, 4-chloro-2-butenyl, 4-chloro-2-butynyl, 1-cyclopropylethyl, 1-cyclopentylethyl, 2-methoxyethyl, 2-n-propoxyethyl, 2-isopropoxyethyl, 2-allyloxyethyl, 2-(2-chloroethoxy)ethyl, 2-benzyloxyethyl, 1-methyl-2-methoxyethyl, 1-methyl-2-n-butoxyethyl or 1-methyl-2-phenoxyethyl. Preferred are the compounds of teh formula (I) wherein X and Y are independently fluorine, chlorine, bromine, iodine, methy, ethyl, n-propyl, vinyl, 1-propenyl, 2-propenyl, ethynyl, methoxy, ethoxy, cyano, 1,2-dibromoethyl, methoxymethyl, methoxycarbonyl, dimethoxymethyl, diethoxymethyl, acetyl or methoxyiminomethyl, Z is oxygen, R.sup.1 is methyl, ethyl, allyl, propargyl, difluoromethyl, 2-fluoroethyl, 2,2,2-trifluoroethyl or 2-chloroethyl, R.sup.2 is methyl, ethyl, isopropyl, sec-butyl, allyl, 1-ethylpropyl, 1-methyl-2-propenyl, 2-butenyl, propargyl, 1-methyl-2-propynyl, 1-ethyl-2-propynyl, 2-butynyl, 1-methyl-3-butynyl, 2-cyanoethyl, 2-fluoroethyl, 1-fluoromethyl-2-fluoroethyl, 1-chloromethylethyl, 1-methoxymethyl-2-chloroethyl, 4-chloro-2-butynyl, 1-cyclopropylethyl, 2-(2-chloroethoxy)ethyl, 1-methyl-2-methoxyethyl or 1-methyl-2-n-butoxyethyl.
Particularly preferred are the compounds of the formula (I) wherein X and Y are each fluorine, chlorine, bromine, methoxymethyl, methyl, ethyl or n-propyl, Z is oxygen, R.sup.1 is ethyl, allyl, propargyl, 2-fluoroethyl, 2,2,2-trifluoroethyl or 2-chloroethyl and R.sup.2 is methyl, ethyl, isopropyl, sec-butyl, allyl, 1-methyl-2-propenyl, propargyl, 1-methyl-2-propynyl, 2-butynyl, 2-cyanoethyl, 4-chloro-2-butynyl or 1-methyl-2-methoxyethyl and the compounds of the formula (I) wherein X is fluorine, chlorine, bromine, methoxy or ethoxy, Y is chlorine, bromine, methyl, ethyl, n-propyl, methoxy, ethoxy, cyano, methoxymethyl, methoxycarbonyl, dimethoxymethyl or acetyl, Z is oxygen, R.sup.1 is ethyl, allyl, propargyl, 2-fluoroethyl, 2,2,2-trifluoroethyl or 2-chloroethyl and R.sup.2 is methyl, ethyl, isopropyl, sec-butyl, allyl, 1-methyl-2-propenyl, propargyl, 1-methyl-2-propynyl, 2-butynyl, 2-cyanoethyl, 4-chloro-2-butynyl or 1-methyl-2-methoxyethyl.
More preferred are the compounds of the formula (I) wherein X and Y are each chlorine, methyl or methoxymethyl, Z is oxygen, R.sup.1 is ethyl, allyl, propargyl, 2-fluoroethyl, 2,2,2-trifluoroethyl or 2-chloroethyl, preferably ethyl, and R.sup.2 is methyl, ethyl, isopropyl, sec-butyl, allyl, 1-methyl-2-propenyl, propargyl, 1-methyl-2-propynyl, 2-butynyl, 2-cyanoethyl, 4-chloro-2-butynyl or 1-methyl-2-methoxyethyl and the compounds of the formula (I) wherein X is fluorine, chlorine, bromine, methoxy or ethoxy, Y is chlorine, methyl, methoxycarbonyl, methoxymethyl or cyano, Z is oxygen, R.sup.1 is ethyl, allyl, propargyl, 2-fluoroethyl, 2,2,2-trifluoroethyl or 2-chloroethyl, preferably ethyl, and R.sup.2 is methyl, ethyl, isopropyl, sec-butyl, allyl, 1-methyl-2-propenyl, propargyl, 1-methyl-2-propynyl, 2-butynyl, 2-cyanoethyl, 4-chloro-2-butynyl or 1-methyl-2-methoxyethyl. Most preferred are the followings:
Isopropyl N-(3,5-dichloro-4-ethoxyphenyl)carbamate;
Isopropyl N-(3,5-dimethyl-4-ethoxyphenyl)carbamate;
Propargyl N-(3,5-dimethyl-4-ethoxyphenyl)carbamate;
1-Methyl-2-propenyl N-(3,5-dimethyl-4-ethoxyphenyl)carbamate;
1-Methyl-2-propynyl N-(3,5-dimethyl-4-ethoxyphenyl)carbamate;
1-Methyl-2-methoxyethyl N-(3,5-dimethyl-4-ethoxyphenyl)carbamate;
Isopropyl N-[3,5-dimethyl-4-(2-propynyloxy)phenyl]carbamate;
Isopropyl N-(3-chloro-4-ethoxy-5-methoxyphenyl)carbamate;
Methyl N-(3-chloro-4,5-diethoxyphenyl)carbamate;
Ethyl N-(3-chloro-4,5-diethoxyphenyl)carbamate;
Isopropyl N-(3-chloro-4,5-diethoxyphenyl)carbamate;
sec-Butyl N-(3-chloro-4,5-diethoxyphenyl)carbamate;
Allyl N-(3-chloro-4,5-diethoxyphenyl)carbamate;
Propargyl N-(3-chloro-4,5-diethoxyphenyl)carbamate;
1-Methyl-2-propenyl N-(3-chloro-4,5-diethoxyphenyl)carbamate;
1-Methyl-2-propynyl N-(3-chloro-4,5-diethoxyphenyl)carbamate;
4-Chloro-2-butynyl N-(3-chloro-4,5-diethoxyphenyl)carbamate;
2-Cyanoethyl N-(3-chloro-4,5-diethoxyphenyl)carbamate;
Isopropyl N-[3-chloro-5-ethoxy-4-(2-propenyloxy)phenyl]carbamate;
1-Methyl-2-methoxyethyl N-[3-chloro-5-ethoxy-4-(2-propenyloxy)phenyl]carbamate;
Isopropyl N-[3-chloro-5-ethoxy-4-(2-propynyloxy)phenyl]carbamate;
Isopropyl N-[3-chloro-4-(2-chloroethyloxy)-5-ethoxyphenyl]carbamate;
Isopropyl N-(3-methoxy-4-ethoxy-5-methylphenyl)carbamate;
Methyl N-(3,4-diethoxy-5-methylphenyl)carbamate;
Ethyl N-(3,4-diethoxy-5-methylphenyl)carbamate;
Isopropyl N-(3,4-diethoxy-5-methylphenyl)carbamate;
sec-Butyl N-(3,4-diethoxy-5-methylphenyl)carbamate;
Propargyl N-(3,4-diethoxy-5-methylphenyl)carbamate;
1-Methyl-2-propenyl N-(3,4-diethoxy-5-methylphenyl)carbamate;
1-Methyl-2-propynyl N-(3,4-diethoxy-5-methylphenyl)carbamate;
1-Methyl-2-methoxyethyl N-(3,4-diethoxy-5-methylphenyl)carbamate;
4-Chloro-2-butynyl N-(3,4-diethyoxy-5-methylphenyl)carbamate;
Isopropyl N-(3,4-diethoxy-5-ethylphenyl)carbamate;
Isopropyl N-(3,4-diethoxy-5-vinylphenyl)carbamate;
Isopropyl N-(3,4-diethoxy-5-methoxyphenyl)carbamate;
Isopropyl N-(3,4-diethoxy-5-methoxymethylphenyl)carbamate;
1-Methyl-2-methoxyethyl N-(3,4-diethoxy-5-methoxymethylphenyl)carbamate;
Isopropyl N-(3-chloro-4-ethoxy-5-methoxymethylphenyl)carbamate;
Isopropyl N-(3,4-diethoxy-5-methoxycarbonylphenyl)carbamate;
Isopropyl N-(3-cyano-4,5-diethoxyphenyl)carbamate;
Isopropyl N-(3-methyl-4-ethoxy-5-methoxymethylphenyl)carbamate;
Isopropyl N-(3-methyl-4-ethoxy-5-n-propylphenyl)carbamate;
Isopropyl N-(3,4-diethoxy-5-bromophenyl)carbamate;
Isopropyl N-(3-methyl-4-propynyloxy-5-ethoxyphenyl)carbamate;
Isopropyl N-(3,4-diethoxy-5-acetylphenyl)carbamate;
Isopropyl N-[3,4-diethoxy-5-(1,2-dibromoethyl)phenyl]carbamate;
Isopropyl N-(3-chloro-4-propynyloxy-5-methoxyphenyl)carbamate;
Isopropyl N-(3,4-diethoxy-5-dimethoxymethylphenyl)carbamate;
Isopropyl N-(3-chloro-4-ethoxy-5-n-propylphenyl)carbamate;
Isopropyl N-(3-bromo-4-ethoxy-5-methoxyphenyl)carbamate;
Isopropyl N-(3,5-diethyl-4-ethoxyphenyl)carbamate;
Isopropyl N-(3-chloro-4-ethoxy-5-methylphenyl)carbamate;
Isopropyl N-(3-methyl-4-ethoxy-5-allylphenyl)carbamate;
Isopropyl N-(3-methoxy-4-ethoxy-5-methoxycarbonylphenyl)carbamate;
Isopropyl N-(3-methoxy-4-ethoxy-5-n-propylphenyl)carbamate;
Isopropyl N-(3-ethyl-4-ethoxy-5-methoxymethylphenyl)carbamate;
Isopropyl N-(3-vinyl-4-ethoxy-5-methoxymethylphenyl)carbamate;
Isopropyl N-(3-bromo-4-ethoxy-5-methoxycarbonylphenyl)carbamate;
Isopropyl N-[3-chloro-4-(2-chloroethoxy)-5-methoxymethylphenyl]carbamate;
Isopropyl N-[3-chloro-4-(2-bromoethoxy)-5-methoxymethylphenyl]carbamate;
Isopropyl N-(3-bromo-4-ethoxy-5-methoxymethylphenyl)carbamate;
Isopropyl N-(3-methyl-4-ethoxy-5-methoxycarbonylphenyl)carbamate;
Isopropyl N-(3-chloro-4-ethoxy-5-methoxycarbonylphenyl)carbamate;
Isopropyl N-(3-methyl-4-ethoxy-5-propionylphenyl)carbamate;
Isopropyl N-(3-fluoro-4,5-diethoxyphenyl)carbamate;
Isopropyl N-[3-chloro-4-(2,2,2-trifluoroethoxy)-5-methoxymethylphenyl]carbamate;
Isopropyl N-(3-methoxy-4-ethoxy-5-methoxymethylphenyl)carbamate;
Isopropyl N-(3-chloro-4-allyloxy-5-methoxymethylphenyl)carbamate;
Isopropyl N-(3-chloro-4-propargyloxy-5-methoxymethylphenyl)carbamate;
Isopropyl N-([3-chloro-4-(2-fluoroethoxy)-5-methoxymethylphenyl]carbamate; etc.
The N-phenylcarbamates (I) can be prepared by either one of the following procedures:
Procedure (a):
Reaction of the 3,4,5-trisubstituted aniline (II) with the chloroformate (III).
The reaction is usually carried out in the presence of an inert solvent (e.g. benzene, toluene, xylene, diethyl ether, tetrahydrofuran, dioxane, chloroform, carbon tetrachloride, ethyl acetate, pyridine, dimethylformamide). When desired, the reaction may be performed in the presence of a dehydrohalogenating agent (e.g. pyridine, triethylamine, diethylaniline, sodium hydroxide, potassium hydroxide) so as to obtain the objective compound (I) in a high yield. The reaction may be accomplished at a temperature of 0.degree. to 150.degree. C. instantaneously or within 12 hours.
Procedure (b):
Reaction of the 3,4,5-trisubstituted phenyl isocyanate (IV) with the alcohol or thiol (V).
The reaction is usually carried out in the absence or presence of an inert solvent (e.g. benzene, toluene, xylene, diethyl ether, tetrahydrofuran, dioxane, N,N-dimethylformamide, chloroform, carbon tetrachloride). When desied, a catalyst (e.g. triethylamine, diethylaniline, 1,4-diazabicyclo(2,2,2)octane) may be used. The reaction is normally accomplished at a temperature of 0.degree. to 50.degree. C. instantaneously or within 12 hours.
In case of the N-phenylcarbamates of the formula (I) wherein at least one of X and Y is a hydroxyiminomethyl group or a lower alkoxyiminomethyl group, it may be prepared by the following procedure (Procedure (c)): reacting the benzaldehyde (VI) with an equimolar or excess amount of hydroxylamine or lower alkoxyamine in an inert solvent (e.g. methanol, ethanol). The reaction may be brought to completion in about 0.5 to 12 hours. For preparation of the N-phenylcarbamates of the formula (I) wherein both of X and Y are hydroxyiminomethyl groups or lower alkoxyiminomethyl groups, there may be used as the starting material the benzaldehyde of the formula (VI) wherein Y is a formyl group.
The 3,4,5-trisubstituted aniline (II) used as the starging material in Procedure (a) can be prepared by reducing a nitrobenzene of the formula: ##STR8## wherein X, Y and R.sup.1 are each as defined above, which is obtainable by reacting a nitrophenol of the formula: ##STR9## wherein X and Y are each as defined above with a reagent of the formula: A--R.sup.1 wherein A is a tosyloxy or mesyloxy group or a halogen atom and R.sup.1 is as defined above.
The reaction of the nitrophenol (VIII) with the reagent may be carried out in an inert solvent such as water, benzene, toluene, xylene, diethyl ether, tetrahydrofuran, dioxane, chloroform, tetrachloromethane, ethyl acetate, ethanol, isopropanol or dimethylformamide, when desired, in the presence of a base such as pyridine, triethylamine, sodium hydroxide, potassium hydroxide or sodium carbonate. If necessary, the reaction mass may be heated or cooled. The reaction may be accomplished within 0.5 to 12 hours to give the objective compound in a high yield.
The reduction of the nitrobenzene (VII) is usually carried out by a conventional reduction technique such as catalytic reduction with platinum oxide, Raney nickel, platinum black or palladium on carbon, reduction in acidic media, for example, in water containing hydrogen chloride, sulfuric acid or acetic acid, using tin, stannous chloride or iron, or reduction in basic media, for example, in methanol or ethanol, using sodium sulfide or sodium hydrosulfide.
The nitrophenol (VIII) can be prepared by a known method [Bavin and Scott: Can. J. Chem., 36, 1284 (1958)].
The 3,4,5-trisubstituted phenyl isocyanate (IV) emplyed as the starting material in Procedure (b) may be prepared by reacting the 3,4,5-trisubstituted aniline (II) with phosgene. This reaction is usually carried out in the presence of an inert solvent (e.g. benzene, toluene, xylene, ethyl acetate) at a temperature of 50.degree. C. to the refluxing temperature of the solvent. The reaction may be accomplished instantaneously or within 12 hours.
The procedures for preparation of the N-phenylcarbamates (I) are illustratively shown in the following Examples.





EXAMPLE 1
Preparation of isopropyl N-(3,5-dichloro-4-methoxyphenyl)carbamate according to Procedure (a):
3,5-Dichloro-4-methoxyaniline (1.8 g) and diethylaniline (1.5 g) were dissolved in benzene (20 ml). To the resultant solution was dropwise added isopropyl chloroformate (1.2 g) in 5 minutes under ice-cooling. After being allowed to stand at room temperature for 12 hours, the reaction mixture was poured into ice-water and extracted with ethyl acetate. The extract was washed with water, dried over magnesium sulfate and concentrated under reduced pressure. The residue was purified by silica gel chromatography using a mixture of benzene and tetrahydrofuran as the eluent to give isopropyl N-(3,5-dichloro-4-methoxyphenyl)carbamate (Compound No. 2) (2.4 g) in a yield of 91.8%. M.P., 107.5.degree.-108.degree. C.
Elementary analysis: Calcd. for C.sub.11 H.sub.13 Cl.sub.2 NO.sub.3 : N, 5.02%; C, 47.38%; H, 4.69%; Cl, 25.44%. Found: N, 5.11%; C, 47.52%; H, 4.76%; Cl, 25.49%.
EXAMPLE 2
Preparation of isopropyl N-(3-bromo-5-chloro-4-methoxyphenyl)carbamate according to Procedure (b):
A mixture of 3-bromo-5-chloro-4-methoxyaniline (13.0 g) in toluene (100 ml) was dropwise added to a toluene solution containing 20 g of phosgene at 10.degree. to 20.degree. C. The resulting mixture was gradually heated and, after being refluxed for 30 minutes, cooled to room temperature. The solvent was removed by distillation under reduced pressure to give 3-bromo-5-chloro-4-methoxyphenyl isocyanate (14.4 g). The thus obtained crude substance was added to an isopropanol solution (50 ml) containing triethylamine (1 g). The resultant mixture was allowed to stand at room temperature for 12 hours, poured into ice-water and extracted with ethyl acetate. The extract was washed with water, dried over magnesium sulfate and concentrated under reduced pressure. The residue was purified by silica gel chromatography using a mixture of benzene and tetrahydrofuran as the eluent to give isopropyl N-(3-bromo-5-chloro-4-methoxyphenyl)carbamate (Compound No. 33) (16.4 g) in a yield of 92% (calculated from the starting 3-bromo-5-chloro-4-methoxyaniline). M.P., 112.degree.-113.5.degree. C.
Elementary analysis: Calcd. for C.sub.11 H.sub.13 NO.sub.3 BrCl: N, 4.33%; C, 40.87%; H, 4.05%; Br, 24.72%; Cl, 10.97%. Found: N, 4.35%; C, 40.84%; H, 3.91%; Br, 25.06%; Cl, 11.20%.
EXAMPLE 3
Preparation of isopropyl N-(3-ethyl-4-ethoxy-5-chlorophenyl)carbamate according to Procedure (a):
3-Ethyl-4-ethoxy-5-chloroaniline (1.9 g) and diethylaniline (1.5 g) were dissolved in toluene (20 ml). To the resultant solution was dropwise added isopropyl chloroformate (1.2 g) in 5 minutes under ice-cooling. After being allowed to stand at room temperature for 12 hours, the reaction mixture was poured into ice-water and extracted with toluene. The extract was washed with water, dried over magnesium sulfate and concentrated under reduced pressure. The residue was purified by silica gel chromatography using toluene as the eluent to give isopropyl N-(3-ethyl-4-ethoxy-5-chlorophenyl)carbamate (Compound No. 53) (2.4 g) in a yield of 89%. M.P., 79.degree.-80.5.degree. C.
Elementary analysis: Calcd. for C.sub.14 H.sub.20 NO.sub.3 Cl: N, 4.89%; C, 58.69%; H, 7.04%; Cl, 12.38%. Found: N, 4.88%; C, 58.43%; H, 6.97%; Cl, 12.28%.
EXAMPLE 4
Preparation of isopropyl N-(3-ethyl-4-ethoxy-5-methylphenyl)carbamate according to Procedure (b):
A mixture of 3-ethyl-4-ethoxy-5-methylaniline (1.8 g) in toluene (20 ml) was dropwise added to a toluene solution containing 10 g of phosgene at 10.degree. to 20.degree. C. The resulting mixture was gradually heated and, after being refluxed for 30 minutes, cooled to room temperature. The solvent was removed by distillation under reduced pressure to gove 3-ethyl-4-ethoxy-5-methylphenyl isocyanate (2.1 g). The thus obtained crude substance was added to an isopropanol solution (20 ml) containing triethylamine (1 g). The resultant mixture was allowed to stand at room temperature for 12 hours, poured into ice-water and extracted with toluene. The extract was washed with water, dried over magnesium sulfate and concentrated under reduced pressure. The residue was purified by silica gel chromatography using toluene as the eluent to give isopropyl N-(3-ethyl-4-ethoxy-5-methylphenyl)carbamate (Compound No. 93) (2.4 g) in a yield of 91% (calculated from the starting 3-ethyl-4-ethoxy-5-methylaniline). M.P., 68.degree.- 69.5.degree. C.
Elementary analysis: Calcd. for C.sub.15 H.sub.23 NO.sub.3 : N, 5.28%; C, 67.89%; H, 8.74%. Found: N, 5.21%; C, 67.85%; H, 8.96%.
EXAMPLE 5
Preparation of isopropyl N-(3,4-diethoxy-5-methoxyiminomethylphenyl)carbamate according to Procedure (c):
Isopropyl N-(3,4-diethoxy-5-formylphenyl)carbamate (0.6 g) was dissolved in ethanol (20 ml). To the solution was added an aqueous solution (10 ml) containing sodium hydroxide (0.32 g) and methoxyamine hydrochloride (0.66 g). After being allowed to stand for 12 hours, the reaction mixture was concentrated in vacuo, and the residue was dissolved in ethyl acetate. The resultant solution was washed with water, dried over magnesium sulfate and concentrated under reduced pressure. The residue was washed with hexane to give isopropyl N-(3,4-diethoxy-5-methoxyiminomethylphenyl)carbamate (Compound No. 191) (0.61 g) in a yield of 93%. M.P., 110.degree.-111.5.degree. C.
Elementary analysis: Calcd. for C.sub.16 H.sub.24 N.sub.2 O.sub.5 : C, 59.24%; H, 7.46%; N, 8.64%. Found: C, 59.01%; H, 7.56%; N, 8.34%.
According to either one of the above Procedures (a), (b) or (c), the N-phenylcarbamates of the formula (I) as shown in Table 1 can be prepared.
TABLE 1__________________________________________________________________________ ##STR10##Com-pound PhysicalNo. X Y R.sup.1 R.sup.2 Z constant__________________________________________________________________________ 1 Cl Cl CH.sub.3 C.sub.2 H.sub.5 O M.P. 94-95.5.degree. C. 2 Cl Cl CH.sub.3 ##STR11## O M.P. 107.5-108.degr ee. C. 3 Cl Cl CH.sub.3 ##STR12## O M.P. 75.5-76.degree . C. 4 Cl Cl CH.sub.3 ##STR13## O M.P. 85-86.5.degree . C. 5 Cl Cl CH.sub.3 CH.sub.2 C CH O M.P. 123-124.5.degree. C. 6 Cl Cl CH.sub.3 ##STR14## O M.P. 57-58.degree. C. 7 Cl Cl CH.sub.3 ##STR15## O M.P. 72-73.degree. C. 8 Cl Cl CH.sub.3 ##STR16## O M.P. 61-62.degree. C. 9 Cl Cl CH.sub.3 CH.sub.2 CHCHCH.sub.3 O M.P. 75-76.degree. C.10 Cl Cl CH.sub.3 CH.sub.2 CCCH.sub.3 O M.P. 110-111.degree. C.11 Cl Cl CH.sub.3 CH.sub.2 CH.sub.2 Cl O n .sub.D.sup.24.5 1.554112 Cl Cl CH.sub.3 CH.sub.2 CHCHCH.sub. O Cl n .sub.D.sup.22.0 1.564113 Cl Cl CH.sub.3 CH.sub.2CCCH.sub.2 Cl O M.P. 105.5-106.5.degree. C.14 Cl Cl CH.sub.3 ##STR17## O n .sub.D.sup.23.0 1.533015 Cl Cl C.sub.2 H.sub.5 ##STR18## O M.P. 65-65.5.degree . C.16 Cl Cl C.sub.2 H.sub.5 CH.sub.2 CH.sub.2 OCH.sub.3 O M.P. 90-91.degree. C.17 Cl Cl C.sub.2 H.sub.5 CH.sub.2 CH.sub.2 O(n)C.sub.3 H.sub.7 O n .sub.D.sup.24.5 1.530218 Cl Cl C.sub.2 H.sub.5 ##STR19## O n .sub.D.sup.24.5 1.528819 Cl Cl CH.sub.2 CH.sub.2 CH.sub.3 ##STR20## O n .sub.D.sup.24.5 1.525120 Cl Cl CH.sub.2 CHCH.sub.2 ##STR21## O n .sub.D.sup.20.5 1.543921 Cl Cl CH.sub.2 CH.sub.2 OCH.sub.3 ##STR22## O n .sub.D.sup.20.5 1.528322 Cl Cl CH.sub.2 CCH ##STR23## O n .sub.D.sup.20.5 1.551123 Cl Cl CH.sub.2 CH.sub.2 CHCH.sub.2 ##STR24## O n .sub.D.sup.21.3 1.531224 Cl Cl CH.sub.2 CH.sub.2 CCH ##STR25## O n .sub.D.sup.21.5 1.522025 Cl Cl ##STR26## ##STR27## O n .sub.D.sup.20.5 1.542926 Cl Cl CHF.sub.2 CH.sub.3 O M.P. 100-101.degree. C.27 Cl Cl CHF.sub.2 C.sub.2 H.sub.5 O M.P. 72-73.degree. C.28 Cl Cl CHF.sub.2 ##STR28## O M.P. 131-132.degree . C.29 Cl Cl CHF.sub.2 ##STR29## O M.P. 118-119.degree . C.30 Cl Cl CHF.sub.2 ##STR30## O M.P. 114-115.degree . C.31 Cl Cl CHF.sub.2 CH.sub.2 CCCH.sub.2 Cl O M.P. 83.5-84.5.degree. C.32 Cl Cl CH.sub.2 CF.sub.3 ##STR31## O M.P. 133-135.degree . C.33 Cl Br CH.sub.3 ##STR32## O M.P. 112-113.5.degr ee. C.34 Br Br CH.sub.3 CH.sub.3 O M.P. 111-112.degree. C.35 Br Br CH.sub.3 C.sub.2 H.sub.5 O M.P. 109.5-111.degree. C.36 Br Br CH.sub.3 ##STR33## O M.P. 122.5-124.degr ee. C.37 Br Br CH.sub.3 CH.sub.2 CCH O M.P. 114.5-115.degr ee. C.38 Br Br CH.sub.3 ##STR34## O M.P. 56-57.5.degree . C.39 Br Br CH.sub.3 ##STR35## O M.P. 78.5-81.5.degr ee. C.40 Br Br CH.sub.3 CH.sub.2 CHCHCH.sub.3 O M.P. 75-76.degree. C.41 Br Br CH.sub.3 CH.sub.2 CCCH.sub.2 Cl O M.P. 112.5-113.5.degree. C.42 Br Br CHF.sub.2 CH.sub.3 O M.P. 84-85.degree. C.43 Br Br CHF.sub.2 C.sub.2 H.sub.5 O M.P. 136-137.degree. C.44 Br Br CHF.sub.2 ##STR36## O M.P. 157-159.degree . C.45 Br Br CHF.sub.2 CH.sub.2 CCH O M.P. 123.5-124.5.degree. C.46 Br Br CHF.sub.2 ##STR37## O M.P. 135.5-137.degr ee. C.47 Br Br CHF.sub.2 ##STR38## O M.P. 140.5-142.degr ee. C.48 Br Br CHF.sub.2 CH.sub.2 CHCHCH.sub.3 O M.P. 95-97.5.degree. C.49 Br Br CHF.sub.2 ##STR39## O M.P. 110-113.5.degr ee. C.50 Br Br CHF.sub.2 CH.sub.2 CCCH.sub.2 Cl O M.P. 105-106.degree. C.51 Cl CH.sub.3 C.sub.2 H.sub.5 ##STR40## O M.P. 79.5-80.5.degr ee. C.52 Cl CH.sub.3 CHF.sub.2 ##STR41## O M.P. 94-95.degree. C.53 Cl C.sub.2 H.sub.5 C.sub.2 H.sub.5 ##STR42## O M.P. 79-80.5.degree . C.54 Cl CH.sub.2 CH.sub.2 CH.sub.3 C.sub.2 H.sub.5 ##STR43## O M.P. 71.5-72.degree . C.55 CH.sub.3 CH.sub.3 CH.sub.3 ##STR44## O M.P. 89-90.degree. C.56 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.2 CCCH.sub.2 Cl O M.P. 72-73.degree. C.57 CH.sub.3 CH.sub.3 C.sub.2 H.sub.5 CH.sub.3 O M.P. 60-61.degree. C.58 CH.sub.3 CH.sub.3 C.sub.2 H.sub.5 C.sub.2 H.sub.5 O M.P. 49.5-51.degree. C.59 CH.sub.3 CH.sub.3 C.sub.2 H.sub.5 ##STR45## O M.P. 98-99.degree. C.60 CH.sub.3 CH.sub.3 C.sub.2 H.sub.5 ##STR46## O M.P. 86-87.degree. C.61 CH.sub.3 CH.sub.3 C.sub.2 H.sub.5 ##STR47## O n .sub.D.sup.19 1.510162 CH.sub.3 CH.sub.3 C.sub.2 H.sub.5 CH.sub.2 CCH O M.P. 110-111.degree. C.63 CH.sub.3 CH.sub.3 C.sub.2 H.sub.5 CH.sub.2 CH.sub.2 CCH O M.P. 67-68.degree. C.64 CH.sub.3 CH.sub.3 C.sub.2 H.sub.5 ##STR48## O M.P. 83.5-84.5.degr ee. C.65 CH.sub.3 CH.sub.3 C.sub.2 H.sub.5 ##STR49## O M.P. 103-104.degree . C.66 CH.sub.3 CH.sub.3 C.sub.2 H.sub.5 ##STR50## O M.P. 63.5-65.degree . C.67 CH.sub.3 CH.sub.3 C.sub.2 H.sub.5 ##STR51## O M.P. 68.5-69.5.degr ee. C.68 CH.sub.3 CH.sub.3 C.sub.2 H.sub.5 ##STR52## O M.P. 75.5-76.5.degr ee. C.69 CH.sub.3 CH.sub.3 C.sub.2 H.sub.5 CH.sub.2 CH.sub.2 F O M.P. 71-72.degree. C.70 CH.sub.3 CH.sub.3 C.sub.2 H.sub.5 ##STR53## O M.P. 95-96.degree. C.71 CH.sub.3 CH.sub.3 C.sub.2 H.sub.5 ##STR54## O M.P. 82-83.degree. C.72 CH.sub.3 CH.sub.3 C.sub.2 H.sub.5 CH.sub.2 CH.sub.2 OCH.sub.2 CHCH.sub.2 O n .sub.D.sup.19.5 1.522173 CH.sub.3 CH.sub.3 C.sub.2 H.sub.5 ##STR55## O n .sub.D.sup.22.5 1.505174 CH.sub.3 CH.sub.3 C.sub.2 H.sub.5 ##STR56## O M.P. 82-83.degree. C.75 CH.sub.3 CH.sub.3 C.sub.2 H.sub.5 ##STR57## O M.P. 124-125.degree . C.76 CH.sub.3 CH.sub.3 C.sub.2 H.sub.5 CH.sub.2 CCCH.sub.2 Cl O M.P. 107-108.degree. C.77 CH.sub.3 CH.sub.3 CH.sub.2 CHCH.sub.2 ##STR58## O n .sub.D.sup.19.6 1.522878 CH.sub.3 CH.sub.3 CH.sub.2 CCH ##STR59## O n .sub.D.sup.22.5 1.526179 CH.sub.3 CH.sub.3 CHF.sub.2 ##STR60## O M.P. 51-52.degree. C.80 CH.sub.3 CH.sub.3 CHF.sub.2 ##STR61## O n .sub.D.sup.22 1.490881 CH.sub.3 CH.sub.3 CHF.sub.2 ##STR62## O n .sub.D.sup.22 1.497682 CH.sub.3 CH.sub.2 CH.sub.2 CH.sub.3 C.sub.2 H.sub.5 ##STR63## O n .sub.D.sup.18.5 1.512783 CH.sub.3 CH.sub.2 CHCH.sub.2 C.sub.2 H.sub.5 ##STR64## O n .sub.D.sup.17.5 1.520584 Br F C.sub.2 H.sub.5 ##STR65## O n .sub.D.sup.20.5 1.529985 I I C.sub.2 H.sub.5 ##STR66## O M.P. 107.5-109.degr ee. C.86 CH.sub.3 CH.sub.3 CHF.sub.2 ##STR67## O M.P. 81-82.degree. C.87 CH.sub.3 CH.sub.3 CHF.sub.2 ##STR68## O M.P. 60-61.degree. C.88 CH.sub.3 CH.sub.3 CHF.sub.2 CH.sub.2 CCCH.sub.3 O M.P. 77-78.degree. C.89 CH.sub.3 CH.sub.3 CHF.sub.2 CH.sub.2 CH.sub.2 Br O M.P. 99.5-100.5.degree. C.90 CH.sub.3 CH.sub.3 CHF.sub.2 CH.sub.2 CCCH.sub.2 Cl O M.P. 71-73.degree. C.91 CH.sub.3 CH.sub.3 CHF.sub.2 ##STR69## O M.P. 91-93.degree. C.92 CH.sub.3 CH.sub.3 CHF.sub.2 ##STR70## O n .sub.D.sup.24.5 1.496593 CH.sub.3 C.sub.2 H.sub.5 C.sub.2 H.sub.5 ##STR71## O M.P. 68-69.594 CH.sub.3 C.sub.2 H.sub.5 C.sub.2 H.sub.5 CH.sub.2 CH.sub.2 F O n .sub.D.sup.22.9 1.512295 CH.sub.3 C.sub.2 H.sub.5 C.sub.2 H.sub.5 CH.sub.2 CF.sub.3 O M.P. 80-81.5.degree. C.96 CH.sub.3 C.sub.2 H.sub.5 C.sub.2 H.sub.5 ##STR72## O M.P. 66-68.degree. C.97 CH.sub.3 C.sub.2 H.sub.5 C.sub.2 H.sub.5 ##STR73## O n .sub.D.sup.22.9 1.514998 CH.sub.3 C.sub.2 H.sub.5 CH.sub.2 CH.sub.2 CH.sub.3 ##STR74## O M.P. 68-71.degree. C.99 CH.sub.3 C.sub.2 H.sub.5 CH.sub.2 CH.sub.2 CH.sub.3 CH.sub.2 CCH O n .sub.D.sup.24.6 1.5280100 CH.sub.3 C.sub.2 H.sub.5 CH.sub.2 CHCH.sub.2 CH.sub.2 CHCHCH.sub.2 Cl O n .sub.D.sup.25.0 1.5335101 CH.sub.3 C.sub.2 H.sub.5 CH.sub.2 CCH ##STR75## O n .sub.D.sup.24.5 1.5235102 CH.sub.3 C.sub.2 H.sub.5 CH.sub.2 CH.sub.2 CHCH.sub.2 ##STR76## O n .sub.D.sup.23.5 1.5225103 CH.sub.3 C.sub.2 H.sub.5 ##STR77## ##STR78## O n .sub.D.sup.24.6 1.5262104 C.sub.2 H.sub.5 C.sub.2 H.sub.5 C.sub.2 H.sub.5 CH.sub.3 O M.P. 83.5-85.degree. C.105 C.sub.2 H.sub.5 C.sub.2 H.sub.5 C.sub.2 H.sub.5 ##STR79## O M.P. 87-89.5.degree . C.106 C.sub.2 H.sub.5 C.sub.2 H.sub.5 C.sub.2 H.sub.5 CH.sub.2 CCCH.sub.2 Cl O M.P. 84-86.5.degree. C.107 C.sub.2 H.sub.5 C.sub.2 H.sub.5 CH.sub.2 CH.sub.2 CCH ##STR80## O n .sub.D.sup.23.5 1.5335108 C.sub.2 H.sub.5 C.sub.2 H.sub.5 CH.sub.2 CH.sub.2 OCH.sub.3 ##STR81## O M.P. 67-69.degree. C.109 C.sub.2 H.sub.5 C.sub.2 H.sub.5 CHF.sub.2 ##STR82## O M.P. 89-90.degree. C.110 Cl OCH.sub.3 C.sub.2 H.sub.5 ##STR83## O M.P. 121-122.degree . C.111 Cl OCH.sub.3 CH.sub.2 CCH CH.sub.3 O n .sub.D.sup.22 1.5619112 Cl OCH.sub.3 CH.sub.2 CCH ##STR84## O M.P. 72-73.degree. C.113 Br OCH.sub.3 C.sub.2 H.sub.5 ##STR85## O M.P. 144.5-145.degr ee. C.114 Br OCH.sub.3 C.sub.2 H.sub.5 CH.sub.2 CCCH.sub.2 Cl O n .sub.D.sup.19.7 .5685115 Cl OC.sub.2 H.sub.5 C.sub.2 H.sub.5 CH.sub.3 O M.P. 98.5-99.5.degree. C.116 Cl OC.sub.2 H.sub.5 C.sub.2 H.sub.5 C.sub.2 H.sub.5 O M.P. 110-111.degree. C.117 Cl OC.sub.2 H.sub.5 C.sub.2 H.sub.5 ##STR86## O M.P. 113-115.degree . C.118 Cl OC.sub.2 H.sub.5 C.sub.2 H.sub.5 ##STR87## O M.P. 94-95.degree. C.119 Cl OC.sub.2 H.sub.5 C.sub.2 H.sub.5 CH.sub.2 CHCH.sub.2 O M.P. 89-90.degree. C.120 Cl OC.sub.2 H.sub.5 C.sub.2 H.sub.5 CH.sub.2 CCH O M.P. 98.5-99.5.degree. C.121 Cl OC.sub. 2 H.sub.5 C.sub.2 H.sub.5 ##STR88## O n .sub.D.sup.18.0 1.5172122 Cl OC.sub.2 H.sub.5 C.sub.2 H.sub.5 ##STR89## O n .sub.D.sup.19.5 1.5121123 Cl OC.sub.2 H.sub.5 C.sub.2 H.sub.5 ##STR90## O M.P. 90-91.degree. C.124 Cl OC.sub.2 H.sub.5 C.sub.2 H.sub.5 ##STR91## O M.P. 120.5-122.degr ee. C.125 Cl OC.sub.2 H.sub.5 C.sub.2 H.sub.5 ##STR92## O n .sub.D.sup.17.0 1.5191126 Cl OC.sub.2 H.sub.5 C.sub.2 H.sub.5 ##STR93## O n .sub.D.sup.16.5 1.5186127 Cl OC.sub.2 H.sub.5 C.sub.2 H.sub.5 ##STR94## O M.P. 61-62.degree. C.128 Cl OC.sub.2 H.sub.5 C.sub.2 H.sub.5 CH.sub.2 CCCH.sub.2 Cl O n .sub.D.sup.20.5 1.5466129 Cl OC.sub.2 H.sub.5 C.sub.2 H.sub.5 ##STR95## O n .sub.D.sup.18.0 1.5206130 Cl OC.sub.2 H.sub.5 C.sub.2 H.sub.5 ##STR96## O n .sub.D.sup.17 1.5140131 Cl OC.sub.2 H.sub.5 C.sub.2 H.sub.5 CH.sub.2 CH.sub.2 C N O M.P. 100.5-101.5.degree. C.132 Cl OC.sub.2 H.sub.5 CH.sub.2 CHCH.sub.2 ##STR97## O M.P. 56-57.degree. C.133 Cl OC.sub.2 H.sub.5 CH.sub.2 CHCH.sub.2 ##STR98## O n .sub.D.sup.18.5 1.5331134 Cl OC.sub.2 H.sub.5 CH.sub.2 CCH ##STR99## O n .sub.D.sup.19.5 1.5202135 Cl OC.sub.2 H.sub.5 CH.sub.2 CHCHCH.sub.3 ##STR100## O n .sub.D.sup.22.0 1.5198136 Cl OC.sub.2 H.sub.5 CH.sub.2 CH.sub.2 Cl ##STR101## O n .sub.D.sup.20.0 1.5323137 Br OC.sub.2 H.sub.5 C.sub.2 H.sub.5 ##STR102## O M.P. 115.5-116.5.de gree. C.138 CH.sub.3 OCH.sub.3 C.sub.2 H.sub.5 ##STR103## O M.P. 116.5-118.degr ee. C.139 CH.sub.3 OC.sub.2 H.sub.5 C.sub.2 H.sub.5 CH.sub.3 O n .sub.D.sup.20.5 1.5212140 CH.sub.3 OC.sub.2 H.sub.5 C.sub.2 H.sub.5 C.sub.2 H.sub.5 O M.P. 69-70.degree. C.141 CH.sub.3 OC.sub.2 H.sub.5 C.sub.2 H.sub.5 ##STR104## O M.P. 86-87.5.degree . C.142 CH.sub.3 OC.sub.2 H.sub.5 C.sub.2 H.sub.5 ##STR105## O M.P. 76-77.degree. C.143 CH.sub.3 OC.sub.2 H.sub.5 C.sub.2 H.sub.5 CH.sub.2 CCH O M.P. 85.5-86.5.degree. C.144 CH.sub.3 OC.sub.2 H.sub.5 C.sub.2 H.sub.5 ##STR106## O M.P. 74-75.degree. C.145 CH.sub.3 OC.sub.2 H.sub.5 C.sub.2 H.sub.5 ##STR107## O M.P. 121-122.5.degr ee. C.146 CH.sub.3 OC.sub.2 H.sub.5 C.sub.2 H.sub.5 ##STR108## O M.P. 57-59.degree. C.147 CH.sub.3 OC.sub.2 H.sub.5 C.sub.2 H.sub.5 ##STR109## O n .sub.D.sup.17.5 1.5425148 CH.sub.3 OC.sub.2 H.sub.5 C.sub.2 H.sub.5 CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 Cl O M.P. 98-99.5.degree. C.149 CH.sub.3 OC.sub.2 H.sub.5 C.sub.2 H.sub.5 ##STR110## O M.P. 63-64.5.degree . C.150 CH.sub.3 OC.sub.2 H.sub.5 C.sub.2 H.sub.5 ##STR111## O M.P. 135.5-137.degr ee. C.151 CH.sub.3 OC.sub.2 H.sub.5 C.sub.2 H.sub.5 CH.sub.2 CCCH.sub.Cl O n .sub.D.sup.19.5 1.5361152 CH.sub.3 OC.sub.2 H.sub.5 CH.sub.2 CCH ##STR112## O n .sub.D.sup.17.5 1.5112153 C.sub.2 H.sub.5 OCH.sub.3 CH.sub.3 ##STR113## O M.P. 80.5-81.degree . C.154 C.sub.2 H.sub.5 OCH.sub.3 CH.sub.3 CH.sub.2 C CCH.sub.3 O n .sub.D.sup.23.2 1.5375155 C.sub.2 H.sub.5 OCH.sub.3 CH.sub.3 ##STR114## O n .sub.D.sup.25.5 1.5092156 CHCH.sub.2 OCH.sub.3 CH.sub.3 ##STR115## O M.P. 105.5-107.degr ee. C.157 C.sub.2 H.sub.5 OC.sub.2 H.sub.5 C.sub.2 H.sub.5 ##STR116## O M.P. 100-101.degree . C.158 CH.sub.2 CH.sub.2 CH.sub.3 OC.sub.2 H.sub.5 C.sub.2 H.sub.5 ##STR117## O M.P. 114-115.degree . C.159 CHCHCH.sub.3 OC.sub.2 H.sub.5 C.sub.2 H.sub.5 ##STR118## O M.P. 89-98.degree. C.160 CHCH.sub.2 OC.sub. 2 H.sub.5 C.sub.2 H.sub.5 ##STR119## O M.P. 127.5-128.5.de gree. C.161 CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3 OC.sub.2 H.sub.5 C.sub.2 H.sub.5 ##STR120## O M.P. 76-77.degree. C.162 OCH.sub.3 OCH.sub.3 CH.sub.3 ##STR121## O M.P. 121.5-122.5.de gree. C.163 OCH.sub.3 OCH.sub.3 C.sub.2 H.sub.5 ##STR122## O M.P. 163-164.5.degr ee. C.164 OCH.sub.3 OCH.sub.3 C.sub.2 H.sub.5 CH.sub.2 CHCHCH.sub.3 O M.P. 112.5-113.5.degree. C.165 OCH.sub.3 OCH.sub.3 C.sub.2 H.sub.5 ##STR123## O M.P. 138.degree. C. (decomp.)166 OCH.sub.3 OC.sub.2 H.sub. 5 C.sub.2 H.sub.5 ##STR124## O M.P. 124-125.degree . C.167 OC.sub.2 H.sub.5 OC.sub.2 H.sub.5 C.sub.2 H.sub.5 ##STR125## O M.P. 147-149.degree . C.168 CH.sub.2 OCH.sub.3 OC.sub.2 H.sub.5 C.sub.2 H.sub.5 ##STR126## O M.P. 107-108.degree . C.169 CH.sub.2 OCH.sub.3 OC.sub.2 H.sub.5 C.sub.2 H.sub.5 ##STR127## O M.P. 61-66.degree. C.170 CH.sub.2 OC.sub.2 H.sub.5 OC.sub.2 H.sub.5 C.sub.2 H.sub.5 CH.sub.2 CCCH.sub.3 O M.P. 79.5-80.5.degree. C.171 CH.sub.2 OCH.sub.2 CHCH.sub.2 OC.sub.2 H.sub.5 C.sub.2 H.sub.5 ##STR128## O M.P. 68.5-69.degree . C.172 CH.sub.2 OCH.sub.2 CCH OC.sub.2 H.sub.5 C.sub.2 H.sub.5 CH.sub.2 CHCHCH.sub.3 O n .sub.D.sup.24.0 1.5279173 CH.sub.2 OCH.sub.2 CH.sub.2 F OC.sub.2 H.sub.5 C.sub.2 H.sub.5 CH.sub.2 CCCH.sub.2 Cl O n .sub.D.sup.22.5 1.5277174 CH.sub.2 OCH.sub.3 Cl C.sub.2 H.sub.5 ##STR129## O n .sub.D.sup.19.7 1.5221; M.P. 65-67.degree. C.175 ##STR130## OC.sub.2 H.sub.5 C.sub.2 H.sub.5 ##STR131## O M.P. 116-118.degree . C.176 ##STR132## OC.sub.2 H.sub.5 C.sub.2 H.sub.5 CH.sub.2 CHCHCH.sub.2 Cl O M.P. 64-65.degree. C.177 ##STR133## OC.sub.2 H.sub.5 C.sub.2 H.sub.5 ##STR134## O M.P. 110-111.degree . C.178 ##STR135## OC.sub.2 H.sub.5 C.sub.2 H.sub.5 ##STR136## O M.P. 118-119.degree . C.179 ##STR137## OC.sub.2 H.sub.5 C.sub.2 H.sub.5 ##STR138## O M.P. 124-125.degree . C.180 CH.sub.2 OCH.sub.3 CH.sub.3 C.sub.2 H.sub.5 C.sub.2 H.sub.5 O n .sub.D.sup.17 1.5198181 C N OC.sub.2 H.sub.5 C.sub.2 H.sub.5 ##STR139## O M.P. 108.5-109.5.de gree. C.182 CN CH.sub.3 C.sub.2 H.sub.5 ##STR140## O n .sub.D.sup.20 1.5265183 CH.sub.2 CN OC.sub.2 H.sub.5 C.sub.2 H.sub.5 ##STR141## O M.P. 101-103.degree . C.184 CH.sub.2 CH.sub.2 CN OC.sub.2 H.sub.5 C.sub.2 H.sub.5 ##STR142## O n .sub.D.sup.16.7 1.5089185 CHCHCN OC.sub.2 H.sub.5 C.sub.2 H.sub.5 ##STR143## O M.P. 97-100.degree. C.186 ##STR144## OC.sub.2 H.sub.5 C.sub.2 H.sub.5 ##STR145## O M.P. 103.5-105.degr ee. C.187 ##STR146## OC.sub.2 H.sub.5 C.sub.2 H.sub.5 ##STR147## O n .sub.D.sup.17.2 1.5145188 ##STR148## OC.sub.2 H.sub.5 C.sub.2 H.sub.5 ##STR149## O n .sub.D.sup.17.2 1.5072189 ##STR150## OC.sub.2 H.sub.5 C.sub.2 H.sub.5 ##STR151## O M.P. 97-99.degree. C.190 CHNOH OC.sub.2 H.sub.5 C.sub.2 H.sub.5 ##STR152## O M.P. 172-173.5.degr ee. C.191 CHNOCH.sub.3 OC.sub.2 H.sub.5 C.sub.2 H.sub.5 ##STR153## O M.P. 110-111.5.degr ee. C.192 CCH OC.sub.2 H.sub.5 C.sub.2 H.sub.5 ##STR154## O M.P. 154.5-156.degr ee. C.193 ##STR155## OC.sub.2 H.sub.5 C.sub.2 H.sub.5 ##STR156## O M.P. 111-121.degree . C.194 ##STR157## OC.sub.2 H.sub.5 C.sub.2 H.sub.5 ##STR158## O M.P. 187-192.degree . C.195 ##STR159## OC.sub.2 H.sub.5 C.sub.2 H.sub.5 ##STR160## O M.P. 141-143.degree . C.196 ##STR161## OC.sub.2 H.sub.5 C.sub.2 H.sub.5 ##STR162## O M.P. 88-90.degree. C.197 CH.sub.2 OH OC.sub.2 H.sub.5 C.sub.2 H.sub.5 ##STR163## O M.P. 117-118.degree . C.198 CH.sub.2 OH OC.sub.2 H.sub.5 C.sub.2 H.sub.5 ##STR164## O M.P. 86-87.5.degree . C.199 CH.sub.3 CH.sub.3 C.sub.2 H.sub.5 C.sub.2 H.sub.5 S n .sub.D.sup.20 1.5623200 CH.sub.3 CH.sub.3 C.sub.2 H.sub.5 ##STR165## S M.P. 73.5-75.degree . C.201 OC.sub.2 H.sub.5 Cl C.sub.2 H.sub.5 ##STR166## S M.P. 70-71.5.degree . C.202 OC.sub.2 H.sub.5 Cl C.sub.2 H.sub.5 ##STR167## S M.P. 80.5-81.5.degr ee. C.203 OC.sub.2 H.sub.5 CH.sub.3 C.sub.2 H.sub.5 C.sub.2 H.sub.5 S M.P. 84.5-85.5.degree. C.204 OC.sub.2 H.sub.5 CH.sub.3 C.sub.2 H.sub.5 ##STR168## S M.P. 71-72.degree. C.205 OC.sub.2 H.sub.5 CH.sub.3 C.sub.2 H.sub.5 ##STR169## S M.P. 84.5-85.5.degr ee. C.206 CH.sub.3 CH.sub.3 CH.sub.3 ##STR170## O M.P. 67.5-68.5.degr ee. C.207 CH.sub.3 CH.sub.3 CH.sub.3 ##STR171## O n .sub.D .sup.25 1.5269208 CH.sub.2 OCH.sub.3 CH.sub.3 C.sub.2 H.sub.5 ##STR172## O n .sub.D.sup.18.5 1.5132; M.P. 68-69.degree. C.209 CH.sub.2 OCH.sub.3 CH.sub.3 C.sub.2 H.sub.5 CH.sub.3 O n .sub.D.sup.17 1.5219210 OCH.sub.3 COOCH.sub.3 C.sub.2 H.sub.5 ##STR173## O M.P. 111-112.degree . C.211 OCH.sub.3 CH.sub.2 CH.sub.2 CH.sub.3 C.sub.2 H.sub.5 ##STR174## O M.P. 75.5-77.degree . C.212 OCH.sub.3 COOCH.sub.3 C.sub.2 H.sub.5 ##STR175## O M.P. 78.5-79.5.degr ee. C.213 OCH.sub.3 CH.sub.2 CH.sub.2 CH.sub.3 C.sub.2 H.sub.5 ##STR176## O M.P. 57-61.degree. C.214 CH.sub.2 OCH.sub.3 C.sub.2 H.sub.5 C.sub.2 H.sub.5 ##STR177## O M.P. 58-61.degree. C.215 CH.sub.2 OCH.sub.3 C.sub.2 H.sub.5 C.sub.2 H.sub.5 ##STR178## O n .sub.D.sup.19.0 1.5118216 CH.sub.2 OCH.sub.3 CHCH.sub.2 C.sub.2 H.sub.5 ##STR179## O n .sub.D.sup.19.0 1.5279217 CH.sub.2 OCH.sub.3 CHCH.sub.2 C.sub.2 H.sub.5 ##STR180## O n .sub.D.sup.19.0 1.5327218 Br COOCH.sub.3 C.sub.2 H.sub.5 ##STR181## O M.P. 86.5-88.degree . C.219 Br COOCH.sub.3 C.sub.2 H.sub. 5 ##STR182## O n .sub.D.sup.19.0 1.5363220 Cl CH.sub.2 OCH.sub.3 CH.sub.3 ##STR183## O n .sub.D.sup.18.0 1.5210221 Cl CH.sub.2 OCH.sub.3 CH.sub.3 ##STR184## O n .sub.D.sup.18.0 1.5246222 Cl CH.sub.2 OCH.sub.3 CH.sub.2 CH.sub.2 CH.sub.3 ##STR185## O n .sub.D.sup.18.0 1.5108223 Cl CH.sub.2 OCH.sub.3 CH.sub.2 CH.sub.2 CH.sub.3 ##STR186## O n .sub.D.sup.18.0 1.5101224 Cl CH.sub.2 OCH.sub.3 CH.sub.2 CH.sub.2 Cl ##STR187## O n .sub.D.sup.21.0 1.5290225 Cl CH.sub.2 OCH.sub.3 CH.sub.2 CH.sub.2 Cl ##STR188## O n .sub.D.sup.21.0 1.5317226 Cl CH.sub.2 OCH.sub.3 CH.sub.2 CH.sub.2 Br ##STR189## O n .sub.D.sup.21.0 1.5425227 Cl CH.sub.2 OCH.sub.3 CH.sub.2 CH.sub.2 Br ##STR190## O n .sub.D.sup.21.0 1.5421228 Br CH.sub.2 OCH.sub.3 C.sub.2 H.sub.5 ##STR191## O n .sub.D.sup.17.3 1.5380229 Br CH.sub.2 OCH.sub.3 C.sub.2 H.sub.5 ##STR192## O n .sub.D.sup.17.3 1.5352230 CH.sub.3 COOCH.sub.3 C.sub.2 H.sub.5 ##STR193## O M.P. 78-81.degree. C.231 CH.sub.3 COOCH.sub.3 C.sub.2 H.sub.5 ##STR194## O n .sub.D.sup.23.2 1.5149232 Cl COOCH.sub.3 C.sub.2 H.sub.5 ##STR195## O M.P. 82-84.degree. C.233 CH.sub.3 ##STR196## C.sub.2 H.sub.5 ##STR197## O n .sub.D.sup.25.5 1.5163234 CH.sub.3 ##STR198## C.sub.2 H.sub.5 ##STR199## O n .sub.D.sup.25.5 1.5158235 F OC.sub.2 H.sub.5 C.sub.2 H.sub.5 ##STR200## O M.P. 80-83.degree. C.236 OCH.sub.3 OC.sub.2 H.sub.5 CH.sub. 2 CCH ##STR201## O M.P. 107-109.degree . C.237 OCH.sub.3 OC.sub.2 H.sub.5 CH.sub.2 CHCH.sub.2 ##STR202## O M.P. 93-95.degree. C.238 OCH.sub.3 CH.sub.2 OCH.sub.3 CH.sub.2 CHCH.sub.2 ##STR203## O n .sub.D.sup.25.9 1.5204239 OCH.sub.3 CH.sub.2 OCH.sub.3 CH.sub.2 CCH ##STR204## O n .sub.D.sup.25.9 1.5238240 Cl CH.sub.2 OCH.sub.3 CH.sub.2 CF.sub.3 ##STR205## O n .sub.D.sup.25.5 1.4919241 Cl CH.sub.2 OCH.sub.3 CH.sub.2 OCH.sub.3 ##STR206## O n .sub.D.sup.25.5 1.5160242 F CH.sub.2 OCH.sub.3 C.sub.2 H.sub.5 ##STR207## O n .sub.D.sup.29.1 1.4992243 Cl CH.sub.2 OCH.sub.3 C.sub.2 H.sub.5 ##STR208## O n .sub.D.sup.24.6 1.5490244 Cl CH.sub.2 OCH.sub.3 C.sub.2 H.sub.5 CH.sub.2 CCH O n .sub.D.sup.24.6 1.5373245 OCH.sub.3 CH.sub.2 OCH.sub.3 C.sub.2 H.sub.5 ##STR209## O M.P. 90-91.5.degree . C.246 OCH.sub.3 CH.sub.2 OCH.sub.3 C.sub.2 H.sub.5 ##STR210## O n .sub.D.sup.25.2 1.5121247 Cl CH.sub.2 OCH.sub.3 C.sub.2 H.sub.5 CH.sub.2 CH.sub.2 F O n .sub.D.sup.25.2 1.5245248 Cl CH.sub.2 OCH.sub.3 C.sub.2 H.sub.5 ##STR211## O n .sub.D.sup.25.2 1.5353249 Cl CH.sub.2 OCH.sub.3 C.sub.2 H.sub.5 CH.sub.2 CH.sub.2 CCH O n .sub.D.sup.25.2 1.5372250 Cl CH.sub.2 OCH.sub.3 C.sub.2 H.sub.5 ##STR212## O n .sub.D.sup.24.0 1.5403251 Cl CH.sub.2 OCH.sub.3 C.sub.2 H.sub.5 ##STR213## S n .sub.D.sup.24.0 1.5534252 Cl CH.sub.2 OCH.sub.3 C.sub.2 H.sub.5 ##STR214## O n .sub.D.sup. 24.0 .5134253 Cl CH.sub.2 OCH.sub.3 C.sub.2 H.sub.5 CH.sub.2 CCCH.sub.2 Cl O M.P. 66.5-74.degree. C.254 Cl CH.sub.2 OCH.sub.3 C.sub.2 H.sub.5 ##STR215## O n .sub.D.sup.24.0 1.5291255 Cl CH.sub.2 OCH.sub.3 C.sub.2 H.sub.5 ##STR216## O n .sub.D.sup.24.0 1.5192256 Cl CH.sub.2 OCH.sub.3 C.sub.2 H.sub.5 CH.sub.2 CH.sub.2 CN O M.P. 123-126.degree. C.257 Cl CH.sub.2 OCH.sub.3 C.sub.2 H.sub.5 CH.sub.3 O n .sub.D.sup.24.0 1.5349258 Cl CH.sub.2 OCH.sub.3 C.sub.2 H.sub.5 C.sub.2 H.sub.5 O n .sub.D.sup.24.0 1.5295259 Cl CH.sub.2 OCH.sub.3 C.sub.2 H.sub.5 ##STR217## O n .sub.D.sup.24.0 1.5148260 Cl CH.sub.2 OCH.sub.3 C.sub.2 H.sub.5 C.sub.2 H.sub.5 S n .sub.D.sup.24.5 1.5648261 Cl CH.sub.2 OCH.sub.3 C.sub.2 H.sub.5 CH.sub.2 CCCH.sub.3 O n .sub.D.sup.24.5 1.5413262 Cl CH.sub.2 OCH.sub.3 C.sub.2 H.sub.5 CH.sub.2 CHCH.sub.2 O n .sub.D.sup.24.5 1.5340263 Cl CH.sub.2 OCH.sub.3 C.sub.2 H.sub.5 ##STR218## O n .sub.D.sup.24.5 1.5186264 Cl CH.sub.2 OCH.sub.3 C.sub.2 H.sub. 5 ##STR219## O M.P. 72-74.degree. C.265 Cl CH.sub.2 OCH.sub.3 C.sub.2 H.sub.5 ##STR220## O n .sub.D.sup.24.5 1.5283266 Cl CH.sub.2 OCH.sub.3 CH.sub.2 CHCH.sub.2 ##STR221## O n .sub.D.sup.25.0 1.5269267 Cl CH.sub.2 OCH.sub.3 CH.sub.2 CCH ##STR222## O n .sub.D.sup.25.0 1.5311268 Cl CH.sub.2 OCH.sub.3 CH.sub.2 CH.sub.2 F ##STR223## O n .sub.D.sup.25.0 1.5133269 CH.sub.2 OCH.sub.3 CH.sub.2 OH C.sub.2 H.sub.5 ##STR224## O n .sub.D.sup.24.2 1.5080270 Cl CH.sub.2 OCH.sub.3 C.sub.2 H.sub.5 ##STR225## S n .sub.D.sup.24.2 1.5505271 Cl CH.sub.2 OCH.sub.3 C.sub.2 H.sub.5 ##STR226## O n .sub.D.sup.25.5 1.5270272 Cl CH.sub.2 OCH.sub.3 C.sub.2 H.sub.5 ##STR227## O n .sub.D.sup.25.5 1.5501273 CH.sub.2 OCH.sub.3 ##STR228## C.sub.2 H.sub.5 ##STR229## O n .sub.D.sup.28.5 1.5175274 CH.sub.2 OCH.sub.3 ##STR230## C.sub.2 H.sub.5 ##STR231## O M.P. 115-116.degree . C.275 CH.sub.2 OCH.sub.3 ##STR232## C.sub.2 H.sub.5 ##STR233## O M.P. 165-171.degree . C.276 CH.sub.2 OCH.sub.3 ##STR234## C.sub.2 H.sub.5 ##STR235## O M.P. 62-63.degree. C.277 CH.sub.2 OCH.sub.3 ##STR236## C.sub.2 H.sub.5 ##STR237## O n .sub.D.sup.23.5 1.5225278 CH.sub.2 OCH.sub.3 ##STR238## C.sub.2 H.sub.5 ##STR239## O n .sub.D.sup.23.5 1.5170__________________________________________________________________________
In the practical use of the N-phenylcarbamates (I) as fungicides, they may be applied as such or in a formulation forms such as dusts, wettable powders, oil sprays, emulsifiable concentrates, tablets, granules, fine granules, aerosols or flowables. Such formulation form can be prepared in a conventional manner by mixing at least one of the N-phenylcarbamates (I) with an appropriate solid or liquid carrier(s) or diluent(s) and, if necessary, an appropriate adjuvant(s) (e.g. surfactants, adherents, dispersants, stabilizers) for improving the dispersibility and other properties of the active ingredient(s).
Examples of the solid carriers or diluents are botanical materials (e.g. flour, tobacco stalk powder, soybean powder, walnut-shell powder, vegetable powder, saw dust, bran, bark powder, cellulose powder, vegetable extract residue), fibrous materials (e.g. paper, corrugated cardboard, old rags), synthetic plastic powders, clays (e.g. kaolin, bentonite, fuller's earth), talcs, other inorganic materials (e.g. pyrophyllite, sericite, pumice, sulfur powder, active carbon) and chemical fertilizers (e.g. ammonium sulfate, ammonium phosphate, ammonium nitrate, urea, ammonium chloride).
Examples of the liquid carriers or diluents are water, alcohols (e.g. methanol, ethanol), ketones (e.g. acetone, methylethylketone), ethers (e.g. diethyl ether, dioxane, cellosolve, tetrahydrofuran), aromatic hydrocarbons (e.g. benzene, toluene, xylene, methyl naphthalene), aliphatic hydrocarbons (e.g. gasoline, kerosene, lamp oil), esters, nitriles, acid amides (e.g. dimethylformamide, dimethylacetamide), halogenated hydrocarbons (e.g. dichloroethane, carbon tetrachloride), etc.
Examples of the surfactants are alkyl sulfuric esters, alkyl sulfonates, alkylaryl sulfonates, polyethylene glycol ethers, polyhydric alcohol esters, etc. Examples of the adherents and dispersants may include cesein, gelatin, starch powder, carboxymethyl cellulose, gum arabic, alginic acid, lignin, bentonite, molasses, polyvinyl alcohol, pine oil and agar. As the stabilizers, there may be used PAP (isopropyl acid phosphate mixture), TCP (tricresyl phosphate), tolu oil, epoxydized oil, various surfactants, verious fatty acids and their esters, etc.
The foregoing formulations generally contain at least one of the N-phenylcarbamates (I) in a concentration of about 1 to 95% by weight, preferably of 2.0 to 80% by weight. By using the formulations, the N-phenylcarbamates (I) are generally applied in such amounts as 2 to 100 g per 10 are
When only the drug-resistant strains of phytopathogenic fungi are present, the N-phenylcarbamates (I) may be used alone. However, when the drug-sensitive strains are present together with the drug-resistant strains, their alternate use with benzimidazole thiophanate fungicides and/or cyclic imide fungicides or their combined use with benzimidazole thiophanate fungicides and/or cyclic imide fungicides is favorable. In such alternate or combined use, each active ingredient may be employed as such or in conventional agricultural formulation forms. In case of the combined use, the weight proportion of the N-phenylcarbamate (I) and the benzimidazole thiophanate fungicide and/or the cyclic imide fungicide may be from about 1:0.1 to 1:10.0.
Typical examples of the benzimidazole thiophanate fungicides and the cyclic imide fungicides are shown in Table 2.
TABLE 2__________________________________________________________________________Compound Structure Name__________________________________________________________________________ ##STR240## Methyl 1-(butylcarbamoyl)benz- imidazol-2-ylcar bamateB ##STR241## 2-(4-Thiazolyl)benzimidazoleC ##STR242## Methyl benzimidazol-2-ylcarbamateD ##STR243## 2-(2-Furyl)benzimidazoleE ##STR244## 1,2-Bis(3-methoxycarbonyl-2- thioureido)benzene OF ##STR245## 1,2-Bis(3-ethoxycarbonyl-2- thioureido)benzene AG ##STR246## 2-(O,SDimethylphosphoryl- amino)-1-(3'-methoxyc arbonyl-2'- thioureido)benzeneH ##STR247## 2-(O,ODimethylthiophos- phorylamino)-1-(3'-meth oxy- carbonyl-2'-thioureido)benzeneI ##STR248## N(3',5'-Dichlorophenyl)-1,2- dimethylcyclopropa ne-1,2- dicarboximideJ ##STR249## 3-(3',5'-Dichlorophenyl)-1-iso- propylcarbamoyl imida- zolidine-2,4-dioneK ##STR250## 3-(3',5'-Dichlorophenyl)-5- methyl-5-vinyloxazo lidine- 2,4-dioneL ##STR251## Ethyl (RS)3-(3',5'-dichloro- phenyl)-5-methyl-2 ,4-dioxo-oxa- zolidine-5-carboxylate__________________________________________________________________________
In addition, the N-phenylcarbamates (I) may be also used in admixture with other fungicides, herbicides, insecticides, miticides, fertilizers, etc.
When the N-phenylcarbamates (I) are used as fungicides, they may be applied in such amounts as 2 to 100 grams per 10 ares. However, this amount may vary depending upon formulation forms, application times, application methods, application sites, diseases, crops and so on, and therefore, they are not limited to said particular amounts.
Some practical embodiments of the fungicidal composition according to the invention are illustratively shown in the following Examples wherein % and part(s) are by weight.
PREPARATION EXAMPLE 1
Two parts of Compound No. 2, 88 parts of clay and 10 parts of talc were thoroughly pulverized and mixed together to obtain a dust preparation containing 2% of the active ingredient.
PREPARATION EXAMPLE 2
Thirty parts of Compound No. 15, 45 parts of diatomaceous earth, 20 parts of white carbon, 3 parts of sodium laurylsulfate as a wetting agent and 2 parts of calcium ligninsulfonate as a dispersing agent were mixed while being powdered to obtain a wettable powder preparation containing 30% of the active ingredient.
PREPARATION EXAMPLE 3
Fifty parts of Compound No. 5, 45 parts of diatomaceous earth, 2.5 parts of calcium alkylbenzenesulfonate as a wetting agent and 2.5 parts of calcium ligninsulfonate as a dispersing agent were mixed while being powdered to obtain a wettable powder preparation containing 50% of the active ingredient.
PREPARATION EXAMPLE 4
Ten parts of Compound No. 22, 80 parts of cyclohexanone and 10 parts of polyoxyethylene alkylaryl ether as an emulsifier were mixed together to obtain an emulsifiable concentrate preparation containing 10% of the active ingredient.
PREPARATION EXAMPLE 5
Two parts of Compound No. 107, 88 parts of clay and 10 parts of talc are thoroughly pulverized and mixed together to obtain a dust preparation containing 2% of the active ingredient.
PREPARATION EXAMPLE 6
Thirty parts of Compound No. 54, 45 parts of diatomaceous earth, 20 parts of white carbon, 3 parts of sodium laurylsulfate as a wetting agent and 2 parts of calcium ligninsulfonate as a dispersing agent were mixed while being powdered to obtain a wettable powder preparation containing 30% of the active ingredient.
PREPARATION EXAMPLE 7
Fifty parts of Compound No. 164, 45 parts of diatomaceous earth, 2.5 parts of calcium alkylbenzenesulfonate as a wetting agent and 2.5 parts of calcium ligninsulfonate as a dispersing agent were mixed while being powdered to obtain a wettable powder preparation containing 50% of the active ingredient.
PREPARATION EXAMPLE 8
Ten parts of Compound No. 101, 80 parts of cyclohexanone and 10 parts of polyoxyethylene alkylaryl ether as an emulsifier were mixed together to obtain an emulsifiable concentrate preparation containing 10% of the active ingredient.
PREPARATION EXAMPLE 9
Two parts of Compound No. 44, 88 parts of clay and 10 parts of talc were thoroughly pulverized and mixed together to obtain a dust preparation containing 2% of the active ingredient.
PREPARATION EXAMPLE 10
Thirty parts of Compound No. 79, 45 parts of diatomaceous earth, 20 parts of white carbon, 3 parts of sodium laurylsulfate as a wetting agent and 2 parts of calcium ligninsulfonate as a dispersing agent were mixed while being powdered to obtain a wettable powder preparation containing 30% of the active ingredient.
PREPARATION EXAMPLE 11
Fifty parts of Compound No. 29, 45 parts of diatomaceous earth, 2.5 parts of calcium alkylbenzenesulfonate as a wetting agent and 2.5 parts of calcium ligninsulfonate as a dispersing agent were mixed while being powdered to obtain a wettable powder preparation containing 50% of the active ingredient.
PREPARATION EXAMPLE 12
Ten parts of Compound No. 81, 80 parts of cyclohexanone and 10 parts of polyoxyethylene alkylaryl ether as an emulsifier were mixed together to obtain an emulsifiable concentrate preparation containing 10% of the active ingredient.
PREPARATION EXAMPLE 13
One part of Compound No. 15, 1 part of Compound No. I, 88 parts of clay and 10 parts of talc were thoroughly pulverized and mixed together to obtain a dust preparation containing 2% of the active ingredient.
PREPARATION EXAMPLE 14
Two parts of Compound No. 105, 2 parts of Compound No. E, 86 parts of clay and 10 parts of talc were thoroughly pulverized and mixed together to obtain a dust preparation containing 4% of the active ingredient.
PREPARATION EXAMPLE 15
Twenty parts of Compound No. 141, 10 parts of Compound J, 45 parts of diatomaceous earth, 20 parts of white carbon, 3 parts of sodium laurylsulfate as a wetting agent and 2 parts of calcium ligninsulfonate as a dispersing agent were mixed while being powdered to obtain a wettable powder preparation containing 30% of the active ingredient.
PREPARATION EXAMPLE 16
Ten parts of Compound No. 181, 40 parts of Compound No. B, 45 parts of diatomaceous earth, 2.5 parts of calcium alkylbenzenesulfonate as a wetting agent and 2.5 parts of calcium ligninsulfonate as a dispersing agent were mixed while being powdered to obtain a wettable powder preparation containing 50% of the active ingredient.
PREPARATION EXAMPLE 17
Twenty-five parts of Compound No. 54, 50 parts of Compound I, 18 parts of diatomaceous earth, 3.5 parts of calcium alkylbenzenesulfonate as a wetting agent and 3.5 parts of calcium ligninsulfonate as a dispersing agent were mixed while being powdered to obtain a wettable powder preparation containing 75% of the active ingredient.
PREPARATION EXAMPLE 18
Twenty parts of Compound No. 105, 30 parts of Compound No. A, 40 parts of powdery sucrose, 5 parts of white carbon, 3 parts of sodium laurylsulfate as a wettig agnet and 2 parts of calcium ligninsulfonate as a dispersing agent were mixed while being powdered to obtain a wettable powder preparation containing 50% of the active ingredient.
Typical test data indicating the excellent fungicidal activity of the N-phenylcarbamates (I) are shown below. The compounds used for comparison are as follows:
______________________________________Compound Remarks______________________________________Control (a) Synthesized for ##STR252## comparisonControl (b) Synthesized for ##STR253## comparisonControl (c) Synthesized for ##STR254## comparisonControl (d) Synthesized for ##STR255## comparisonControl (e) Synthesized for ##STR256## comparisonControl (f) Synthesized for ##STR257## comparisonControl (g) Synthesized for ##STR258## comparisonControl (h) Synthesized for ##STR259## comparisonControl (i) Agricultural Biological ##STR260## Chemistry, 35, 1707- 1719 (1971)Control (j) Agricultural Biological ##STR261## Chemistry, 35, 1707- 1719 (1971)Control (k) Agricultural Biological ##STR262## Chemistry, 35, 1707- 1719 (1971)Control (l) Agricultural Biological ##STR263## Chemistry, 35, 1707- 1719 (1971)Swep Commercially available ##STR264## herbicideChlorpropham Commercially available ##STR265## herbicideBarban Commercially available ##STR266## herbicideCEPC Commercially available ##STR267## herbicidePropham Commercially available ##STR268## herbicideChlorbufam Commercially available ##STR269## herbicideBenomyl Commercially available ##STR270## fungicideThiophanate-methyl Commercially available ##STR271## fungicideCarbendazim Commercially available ##STR272## fungicideThiabendazole Commercially available ##STR273## fungicideEdifenphos Commercially available ##STR274## fungicide______________________________________
EXPERIMENT 1
Protective activity test on powdery mildew of cucumber (Sphaerotheca fuliginea):
A flower pot of 90 ml volume was filed with sandy soil, and seeds of cucumber (var: Sagami-hanjiro) were sown therein. Cultivation was carried out in a greenhouse for 8 days. Onto the resulting seedlings having cotyledons, the test compound formulated in emulsifiable concentrate or wettable powder and diluted with water was sprayed at a rate of 10 ml per pot. Then, the seedlings were inoculated with a spore suspension of the drug-resistant or drug-sensitive strain of Sphaerotheca fuliginea by spraying and further cultivated in the greenhouse. Ten days thereafter, the infectious state of the plants was observed. The degree of damage was determined in the following manner, and the results are shown in Table 3.
The leaves examined were measured for a percentage of infected area and classified into the corresponding disease indices, 0, 0.5, 1, 2, 4:
______________________________________Disease index Percentage of infected area______________________________________0 No infection0.5 Infected area of less than 5%1 Infected area of less than 20%2 Infected area of less than 50%4 Infected area of not less than 50%______________________________________
The disease severity was calculated according to the following equation: ##EQU1##
The prevention value was calculated according to the following equation: ##EQU2##
TABLE 3______________________________________ Prevention Prevention value when value when Concentration inoculated inoculated of active with drug- with drug-Compound ingredient resistant sensitiveNo. (ppm) strain (%) strain (%)______________________________________ 2 200 100 0 6 200 100 0 7 200 100 013 200 97 015 200 100 019 200 100 020 200 100 022 200 100 024 200 100 028 200 97 029 200 100 031 200 94 032 200 97 033 200 100 036 200 97 039 200 94 044 200 97 050 200 97 051 200 100 052 200 97 054 200 100 055 200 100 057 200 100 058 200 100 059 200 100 060 200 100 061 200 100 062 200 100 063 200 100 064 200 100 065 200 100 068 200 100 070 200 100 071 200 100 073 200 100 074 200 100 077 200 100 078 200 100 079 200 100 080 200 100 084 200 100 086 200 100 088 200 94 090 200 100 091 200 100 092 200 97 099 200 100 0101 200 100 0102 200 100 0103 200 100 0105 200 100 0109 200 100 0110 200 100 0111 200 100 0112 200 100 0115 200 100 0116 200 100 0117 200 100 0118 200 100 0119 200 100 0120 200 100 0122 200 100 0124 200 100 0127 200 100 0129 200 100 0130 200 100 0131 200 100 0132 200 100 0133 200 100 0134 200 100 0135 200 100 0138 200 100 0140 200 100 0141 200 100 0142 200 100 0143 200 100 0146 200 100 0147 200 100 0152 200 100 0157 200 100 0159 200 100 0165 200 100 0167 200 100 0174 200 100 0181 200 100 0193 200 100 0Control (a) 200 0 0Control (b) 200 0 0Control (c) 200 0 0Control (d) 200 0 0Control (e) 200 0 0Control (f) 200 0 0Control (g) 200 0 0Control (h) 200 0 0Control (i) 200 0 0Control (j) 200 0 0Control (k) 200 0 0Control (l) 200 0 0Swep 200 0 0Chlorpropham 200 0 0Barban 200 25 0CEPC 200 0 0Propham 200 0 0Chlorbufam 200 0 0Benomyl 200 0 100Thiophanate- 200 0 100methylCarbendazim 200 0 100______________________________________
As understood from the results shown in Table 3, the N-phenylkcarbamates (I) of the invention show an excellent preventive effect on the drug-resistant strain but do not show any preventive effect on the tested drug-sensitive strain. To the contrary, commercially available known fungicides such as Benomyl, Thiophanate-methyl and Carbendazim show a notable controlling effect on the drug-sensitive strain but not on the drug-resistant strain. Other tested compounds structurally similar to the N-phenylcarbamates (I) do not show any fungicidal activity on the drug-sensitive strain and the drug-resistant strain.
EXPERIMENT 2
Preventive effect on cercospora leaf spot of sugarbeet (Cercospora beticola):
A flower pot of 90 ml volume was filled with sandy soil, and seeds of sugarbeet (var: Detroit dark red) were sown therein. Cultivation was carried out in a greenhouse for 20 days. Onto the resulting seedlings, the test compound formulated in emulsifiable concentrate or wettable powder and diluted with water was sprayed at a rate of 10 ml per pot. Then, the seedlings were inoculated with a spore suspension of the drug-resistant or drug-sensitive strain of Cercospora beticola by spraying. The pot was covered with a polyvinyl chloride sheet to make a condition of high humidity, and cultivation was continued in the greenhouse for 10 days. The degree of damage was determined in the same manner as in Experiment 1, and the results are shown in Table 4.
TABLE 4______________________________________ Prevention Prevention value when value when Concentration inoculated inoculated of active with drug- with drug-Compound ingredient resistant sensitiveNo. (ppm) strain (%) strain (%)______________________________________ 2 200 100 0 6 200 96 0 7 200 100 0 8 200 100 0 13 200 97 0 15 200 100 0 19 200 100 0 20 200 100 0 22 200 100 0 24 200 100 0 28 200 99 0 29 200 100 0 31 200 94 0 32 200 100 0 33 200 100 0 36 200 97 0 38 200 94 0 40 200 100 0 41 200 100 0 44 200 96 0 47 200 94 0 50 200 100 0 51 200 100 0 52 200 100 0 54 200 100 0 55 200 100 0 57 200 100 0 58 200 100 0 59 200 100 0 60 200 100 0 64 200 100 0 68 200 100 0 74 200 100 0 78 200 100 0 79 200 100 0 80 200 100 0 81 200 96 0 86 200 100 0 88 200 100 0 90 200 100 0 91 200 100 0 92 200 97 0 93 200 100 0 99 200 100 0100 200 100 0102 200 100 0104 200 100 0105 200 100 0107 200 97 0108 200 100 0109 200 100 0110 200 100 0112 200 100 0114 200 100 0116 200 100 0117 200 100 0118 200 100 0129 200 100 0131 200 100 0132 200 100 0134 200 100 0138 200 100 0141 200 100 0142 200 100 0143 200 100 0146 200 100 0155 200 94 0157 200 100 0160 200 100 0164 200 100 0168 200 100 0181 200 100 0188 200 100 0193 200 100 0210 200 100 0211 200 100 0214 200 100 0218 200 100 0219 200 100 0224 200 100 0226 200 100 0228 200 100 0229 200 100 0230 200 100 0232 200 100 0233 200 100 0235 200 100 0236 200 100 0237 200 100 0238 200 100 0240 200 100 0242 200 100 0245 200 100 0247 200 100 0256 200 100 0259 200 100 0Control (a) 200 0 0Control (b) 200 0 0Control (c) 200 0 0Control (d) 200 0 0Control (e) 200 0 0Control (f) 200 0 0Control (g) 200 0 0Control (h) 200 0 0Control (i) 200 0 0Control (j) 200 0 0Control (k) 200 0 0Control (l) 200 0 0Swep 200 0 0Chlorpropham 200 0 0Barban 200 34 0CEPC 200 0 0Propham 200 0 0Chlorbufam 200 0 0Benomyl 200 0 100Thiophanate- 200 0 100methylCarbendazim 200 0 100______________________________________
As understood from the results shown in Table 4, the N-phenylcarbamates (I) of the invention show an excellent preventive effect on the drug-resistant strain but do no show any preventive effect on the tested drug-sensitive strain. To the contrary, commecially available known fungicides such as Benomyl, Thiophanate-methyl and Carbendazim show a notable controlling effect on the drug-sensitive strain but not on the drug-resistant strain. Other tested compounds structurally similar to the N-phenylcarbamates (I) do not show any fungicidal activity on the drug-sensitive strain and the drug-resistant strain.
EXPERIMENT 3
Preventive effect on scab of pear (Venturia nashicola):
A plastic pot of 90 ml volume was filled with sandy soil, and seeds of pear (var: Chojuro) were sown therein. Cultivation was carried out in a greenhouse for 20 days. Onto the resulting seedlings, the test compound formulated in emulsifiable concentrate or wettable powder and diluted with water was sprayed at a rate of 10 ml per pot. Then, the seedlings were inoculated with a spore suspension of the drug-resistant or drug-sensitive strain of Venturia nashicola by spraying. The resulting plants were placed at 20.degree. C. under a condition of high humidity for 3 days and then at 20.degree. C. under irradiation with a fluorescent lamp for 20 days. The degree of damage was determined in the same manner as in Experiment 1, and the results are shown in Table 5.
TABLE 5______________________________________ Prevention Prevention value when value when Concentration inoculated inoculated of active with drug- with drug-Compound ingredient resistant sensitiveNo. (ppm) strain (%) strain (%)______________________________________ 2 200 100 0 3 200 94 0 5 200 91 0 8 200 97 0 9 200 96 010 200 94 013 200 100 014 200 91 015 200 100 019 200 100 020 200 100 022 200 100 024 200 100 026 200 91 027 200 88 029 200 100 030 200 88 031 200 100 035 200 88 038 200 100 042 200 85 043 200 88 044 200 100 045 200 91 046 200 94 047 200 100 048 200 94 049 200 85 051 200 94 053 200 100 055 200 100 064 200 100 065 200 100 068 200 100 081 200 97 087 200 94 089 200 88 098 200 100 0100 200 100 0102 200 100 0103 200 100 0104 200 100 0105 200 100 0106 200 100 0107 200 91 0108 200 100 0110 200 100 0112 200 100 0116 200 100 0117 200 100 0118 200 100 0124 200 100 0128 200 100 0132 200 100 0134 200 100 0138 200 100 0141 200 100 0143 200 100 0145 200 100 0146 200 100 0153 200 97 0156 200 100 0163 200 100 0164 200 100 0174 200 100 0181 200 100 0Benomyl 200 0 100Thiophanate- 200 0 100methyl______________________________________
As understood from the results shown in Table 5, the N-phenylcarbamates (I) of the invention show an excellent preventive effect on the drug-resistant strain but do not show any preventive effect on the tested drug-sensitive strain. To the contrary, commercially available known fungicides such as Benomyl and Thiophanate-methyl show a notable controlling effect on the drug-sensitive strain but not on the drug-resistant strain.
EXPERIMENT 4
Preventive effect on brown leaf-spot of peanut (Cercospora arachidicola):
A plastic pot of 90 ml volume was filled with sandy soil, and seeds of peanut (var: Chiba hanryusei) were sown therein. Cultivation was carried out in a greenhouse for 14 days. Onto the resulting seedlings, the test compound formulated in emulsifiable concentrate or wettable powder and diluted with water was sprayed at a rate of 10 ml per pot. Then, the seedlings were inoculated with a spore suspension of the drug-resistant or drug-sensitive strain of Cercospora arachidicola by spraying. The resulting plants were covered with a polyvinyl chloride sheet to make a humide condition and cultivated in the greenhouse for 10 days. The degree of damage was determined in the same manner as in Experiment 1, and the results are shown in Table 6.
TABLE 6______________________________________ Prevention Prevention value when value when Concentration inoculated inoculated of active with drug- with drug-Compound ingredient resistant sensitiveNo. (ppm) strain (%) strain (%)______________________________________ 2 200 100 0 6 200 100 0 7 200 100 0 8 200 100 010 200 100 012 200 97 015 200 100 019 200 100 020 200 98 022 200 100 024 200 98 029 200 100 032 200 100 036 200 100 038 200 94 041 200 100 044 200 97 052 200 97 054 200 100 055 200 100 056 200 100 064 200 100 068 200 100 073 200 100 079 200 100 080 200 100 086 200 94 087 200 91 088 200 100 090 200 100 091 200 100 092 200 100 0101 200 100 0102 200 100 0105 200 100 0109 200 100 0110 200 100 0117 200 100 0132 200 100 0134 200 100 0138 200 100 0141 200 100 0142 200 100 0146 200 100 0165 200 97 0181 200 100 0Benomyl 200 0 100Thiophanate- 200 0 100methyl______________________________________
As understood from the results shown in Table 6, the N-phenylcarbamates (I) of the invention show an excellent preventive effect on the drug-resistant strain but do not show any preventive effect on the tested drug-sensitive strain. To the contrary, commercially available known fungicides such as Benomyl and Thiophanate-methyl show a notable controlling effect on the drug-sensitive strain but not on the drug-resistant strain.
EXPERIMENT 5
Preventive effect on gray mold of cucumber (Botrytis cinerea):
Plastic pots of 90 ml volume was filled with sandy soil, and seeds of cucumber (var: Sagami-hanjiro) were sown therein. Cultivation was carried out in a greenhouse for 8 days to obtain cucumber seedlings expanding cotyledons. Onto the resulting seedlings, the test compound formulated in emulsifiable concentrate or wettable powder and diluted with water was sprayed at a rate of 10 ml per pot. After air-drying, the seedlings were inoculated with mycelial disks (5 mm in diameter) of the drug-resistant or drug-sensitive strain of Botrytis cinerea by putting them on the leaf surfaces. After the plants were infected by incubating under high humidity at 20.degree. C. for 3 days, the rates of disease severity were observed. The degree of damage was determined in the same manner as in Experiment 1, and the results are shown in Table 7.
TABLE 7______________________________________ Prevention Prevention value when value when Concentration inoculated inoculated of active with drug- with drug-Compound ingredient resistant sensitiveNo. (ppm) strain (%) strain (%)______________________________________ 1 200 88 0 2 200 100 0 3 200 94 0 4 200 88 0 5 200 91 0 6 200 96 0 7 200 100 0 8 200 97 0 9 200 91 0 10 200 97 0 11 200 84 0 12 200 100 0 13 200 96 0 14 200 88 0 15 200 100 0 16 500 91 0 17 500 88 0 18 500 88 0 19 200 100 0 20 200 100 0 21 200 97 0 22 200 100 0 23 200 88 0 24 200 100 0 25 200 97 0 28 200 97 0 29 200 100 0 31 200 94 0 32 200 97 0 33 200 88 0 34 200 84 0 35 200 91 0 36 200 97 0 37 200 91 0 38 200 94 0 39 200 94 0 40 200 97 0 41 200 100 0 44 200 94 0 47 200 91 0 48 200 88 0 50 200 94 0 51 200 91 0 52 200 97 0 53 200 100 0 54 200 100 0 55 200 100 0 56 200 100 0 57 200 100 0 58 200 100 0 59 200 97 0 60 200 100 0 61 200 88 0 62 200 100 0 63 200 100 0 64 200 100 0 65 200 100 0 66 200 100 0 67 200 100 0 68 200 100 0 69 200 100 0 70 200 100 0 71 200 100 0 72 200 100 0 73 200 100 0 74 200 100 0 75 200 100 0 76 200 100 0 77 200 100 0 78 200 100 0 79 200 100 0 80 200 100 0 81 200 94 0 82 200 100 0 83 200 100 0 84 200 100 0 85 200 100 0 86 200 100 0 88 200 97 0 90 200 100 0 91 200 100 0 92 200 97 0 93 200 94 0 94 200 97 0 95 200 88 0 96 200 100 0 97 200 100 0 98 200 91 0 99 200 97 0100 200 100 0101 200 100 0102 200 100 0103 200 97 0104 200 100 0105 200 100 0106 200 100 0107 200 91 0108 200 100 0109 200 100 0110 200 100 0112 200 100 0113 200 100 0114 200 100 0115 200 100 0116 200 100 0117 200 100 0118 200 100 0119 200 100 0120 200 100 0121 200 100 0122 200 88 0123 200 100 0124 200 100 0125 200 94 0126 200 94 0127 200 100 0128 200 100 0129 200 100 0130 200 100 0131 200 100 0132 200 100 0133 200 100 0134 200 100 0135 200 100 0136 200 100 0137 200 100 0138 200 100 0139 200 100 0140 200 100 0141 200 100 0142 200 100 0143 200 100 0144 200 100 0145 200 100 0146 200 100 0147 200 100 0148 200 100 0149 200 100 0150 200 100 0151 200 100 0152 200 100 0153 200 97 0154 200 88 0155 200 91 0156 200 97 0157 200 100 0158 200 100 0159 200 100 0160 200 100 0161 200 100 0162 200 100 0163 200 100 0164 200 100 0165 200 100 0166 200 100 0167 200 100 0168 200 100 0169 200 100 0170 200 94 0171 200 100 0172 200 100 0173 200 100 0174 200 100 0175 200 100 0176 200 100 0177 500 88 0178 500 88 0179 500 88 0180 200 100 0181 200 100 0182 200 100 0183 200 100 0184 200 100 0185 200 95 0186 200 88 0187 200 100 0188 200 100 0189 200 100 0190 200 100 0191 200 100 0192 200 100 0193 200 100 0194 200 100 0195 200 100 0196 200 100 0197 200 97 0198 200 94 0199 200 100 0200 200 100 0201 200 100 0202 200 100 0203 200 100 0204 200 100 0205 200 100 0206 200 100 0207 200 88 0208 200 100 0209 200 100 0210 200 100 0211 200 100 0212 200 100 0213 200 100 0214 200 100 0215 200 100 0216 200 100 0217 200 100 0218 200 100 0219 200 100 0220 200 100 0221 200 100 0222 200 100 0223 200 100 0224 200 100 0225 200 100 0226 200 100 0227 200 100 0228 200 100 0229 200 100 0230 200 100 0231 200 100 0232 200 100 0233 200 100 0234 200 100 0235 200 100 0236 200 100 0237 200 100 0238 200 100 0239 200 100 0240 200 100 0241 200 100 0242 200 100 0243 200 100 0244 200 100 0245 200 100 0246 200 100 0247 200 100 0248 200 100 0249 200 100 0250 200 100 0251 200 100 0252 200 100 0253 200 100 0254 200 100 0255 200 100 0256 200 100 0257 200 100 0258 200 100 0259 200 100 0260 200 100 0261 200 100 0262 200 100 0263 200 100 0264 200 100 0265 200 100 0266 200 100 0267 200 100 0268 200 100 0269 200 100 0270 200 100 0271 200 100 0272 200 100 0273 200 100 0274 200 100 0275 200 88 0276 200 100 0277 200 100 0278 200 100 0Benomyl 200 0 100Thiophanate- 200 0 100methylThiabendazole 200 0 100______________________________________
As understood from the results shown in Table 7, the N-phenylcarbamates (I) of the invention show an excellent preventive effect on the drug-resistant strain but do not show any preventive effect on the tested drug-sensitive strain. To the contrary, commercially available known fungicides such as Benomyl, Thiophanate-methyl and Thiabendazole show a notable controlling effect on the drug-sensitive strain but not on the drug-resistant strain.
EXPERIMENT 6
Preventive effect on gummy stem blight of cucumber (Mycosphaerella melonis):
Plastic pots of 90 ml volume was filled with sandy soil, and seeds of cucumber (var: Sagami-hanjiro) were sown therein. Cultivation was carried out in a greenhouse for 8 days to obtain cucumber seedlings expanding cotyledons. Onto the resulting seedlings, the test compound formulated in emulsifiable concentrate or wettable powder and diluted with water was sprayed at a rate of 10 ml per pot. After air-drying, the seedlings were inoculated with mycelial disks (5 mm in diameter) of the drug-resistant or drug-sensitive strain of Mycosphaerella melonis by putting them on the leaf surfaces. After the plants were infected by incubating under high humidity at 25.degree. C. for 4 days, the rates of disease severity were observed. The degree of damage was determined in the same manner as in Experiment 1, and the results are shown in Table 8.
TABLE 8______________________________________ Prevention Prevention value when value when Concentration inoculated inoculated of active with drug- with drug-Compound ingredient resistant sensitiveNo. (ppm) strain (%) strain (%)______________________________________ 2 200 100 0 6 200 100 0 7 200 100 0 8 200 100 010 200 100 015 200 100 019 200 100 020 200 100 022 200 100 023 200 91 029 200 100 031 200 97 036 200 100 039 200 97 040 200 100 054 200 100 056 200 100 057 200 100 059 200 100 064 200 100 068 200 100 077 200 100 078 200 100 079 200 100 080 200 100 086 200 100 088 200 97 090 200 100 091 200 100 0101 200 100 0102 200 100 0105 200 100 0109 200 100 0110 200 100 0117 200 100 0124 200 100 0132 200 100 0134 200 100 0138 200 100 0141 200 100 0142 200 100 0146 200 100 0181 200 100 0Benomyl 200 0 100Thiophanate- 200 0 100methyl______________________________________
As understood from the results shown in Table 8, the N-phenylcarbamates (I) of the invention show an excellent preventive effect on the drug-resistant strain but do not show any preventive effect on the tested drug-sensitive strain. To the contrary, commercially available known fungicides such as Benomyl and Thiophanate-methyl show a notable controlling effect on the drug-sensitive strain but not on the drug-resistant strain.
EXPERIMENT 7
Preventive effect on green mold of orange (Penicillium italicum):
Fruits of orange (var: Unshu) were washed with water and dried in the air. The fruits were immersed in a solution of the test compound prepared by diluting an emulsifiable concentrate comprising the test compound with water for 1 minute. After drying in the air, the fruits were inoculated with a spore suspension of the drug-resistant or drug-sensitive strain of Penicillium italicum by spraying and placed in a room of high humidity for 24 days. The degree of damage was determined in the following manner:
The fruits examined were measured for a percentage of infected area and classified into the corresponding indices, 0, 1, 2, 3, 4, 5:
______________________________________Disease index Percentage of infected area______________________________________0 No infection1 Infected area of less than 20%2 Infected area of less than 40%3 Infected area of less than 60%4 Infected area of less than 80%5 Infected area of not less than 80%______________________________________
Calculation of the degree of damage and the prevention value was made as in Experiment 1.
The results are shown in Table 9.
TABLE 9______________________________________ Prevention Prevention value when value when Concentration inoculated inoculated of active with drug- with drug-Compound ingredient resistant sensitiveNo. (ppm) strain (%) strain (%)______________________________________ 2 200 100 0 6 200 100 0 7 200 100 0 8 200 100 013 200 100 015 200 100 019 200 100 020 200 100 022 200 100 024 200 100 028 200 100 029 200 100 036 200 100 038 200 94 040 200 97 051 200 100 055 200 100 056 200 100 064 200 100 068 200 100 073 200 100 078 200 100 079 200 100 090 200 100 099 200 100 0103 200 100 0109 200 100 0110 200 100 0116 200 100 0117 200 100 0118 200 100 0129 200 100 0132 200 100 0134 200 100 0138 200 100 0141 200 100 0146 200 100 0156 200 100 0163 200 94 0181 200 100 0Benomyl 200 0 100Thiophanate- 200 0 100methyl______________________________________
As understood from the results shown in Table 9, the N-phenylcarbamates (I) of the invention show an excellent preventive effect on the drug-resistant strain but do not show any preventive effect on the tested drug-sensitive strain. To the contrary, commercially available known fungicides such as Benomyl and Thiophanate-methyl show a notable controlling effect on the drug-sensitive strain but not on the drug-resistant strain.
EXPERIMENT 8
Preventive effect on rice blast (Pyricularia oryzae):
Plastic pots of 90 ml were filled with a cultured soil for rice plants, and seeds of rice plant (var: Kinki No. 33) were sown therein and cultivated in a greenhouse. Onto the seedlings of 3-leaf stage, the test compound formulated in an emulsifiable concentrate and diluted with water was sprayed to enough cover the leaf surfaces with droplets. After air-drying, the seedlings were inoculated with a spore suspension of Pyricularia oryzae by spraying, followed by incubation at 28.degree. C. for 3 days under a high humid condition. The disease severity were observed and the degree of damage was determined in the same manner as in Experiment 1. The results are shown in Table 10.
TABLE 10______________________________________ Concentration of Prevention active ingredient valueCompound No. (ppm) (%)______________________________________ 28 500 100 46 500 100 47 500 100101 500 97153 1000 99154 1000 95Edifenphos 500 97______________________________________
EXPERIMENT 9
Phytotoxicity to crop plants:
Plastic pots of 150 ml volume were filled with sandy soil, and seeds of wheat (var: Norin No. 61), apple (var: Kogyoku) and peanut (var: Chiba hanryusei) were sown therein. Cultivation was carried out in a greenhouse. Onto the resulting seedlings, the test compound formulated in emulsifiable concentrate or wettable powder and diluted with water was sprayed. After cultivation in the greenhouse for additional 10 days, the phytotoxicity was examined on the following criteria:
______________________________________Extent Observation______________________________________- No abnormality+ Abnormality due to phytotoxicity observed in a part of crop plants++ Abnormality due to phytotoxicity observed in entire crop plants+++ Crop plants withered due to phytotoxicity______________________________________
The results are shown in Table 11.
TABLE 11______________________________________ Concentration of activeCompound ingredient PhytotoxicityNo. (ppm) Wheat Apple Peanut______________________________________ 2 1000 - - - 15 1000 - - - 28 1000 - - - 39 1000 - - - 59 1000 - - - 79 1000 - - -102 1000 - - -108 1000 - - -109 1000 - - -110 1000 - - -117 1000 - - -120 1000 - - -141 1000 - - -145 1000 - - -153 1000 - - -Barban 1000 - ++ ++CEPC 1000 - ++ ++Swep 1000 ++ ++ +______________________________________
As understood from the results shown in Table 11, the N-phenylcarbamates (I) of the invention produce no material phytotoxicity, while commercially available herbicides having a chemical structure similar thereto produce considerable phytotoxicity.
EXPERIMENT 10
Preventive effect on powdery mildew of cucumber (Sphaerotheca fuliginea):
A plastic pot of 90 ml volume was filled with sandy soil, and seeds of cucumber (var: Sagami-hanjiro) were sown therein. Cultivation was carried out in a greenhouse for 8 days. Onto the resulting seedlings having cotyledons, the test compound formulated in emulsifiable concentrate or wettable powder and diluted with water were sprayed at a rate of 10 ml per pot. Then, the seedlings were inoculated with a mixed spore suspension of the drug-resistant and drug-sensitive strain of Sphaerotheca fuliginea by spraying and further cultivated in the greenhouse. Ten days thereafter, the infectious state of the plants was observed. The degree of damage was determined in the same manner as in Experiment 1, and the results are shown in Table 12.
TABLE 12______________________________________ Concentration of Prevention active ingredient valueCompound No. (ppm) (%)______________________________________ 2 100 36 2 20 0 15 100 32 15 20 0 22 100 44 22 20 0 54 100 28 54 20 0 59 100 36 59 20 0105 100 28105 20 0110 100 32110 20 0117 100 36117 20 0141 100 28141 20 0181 100 44181 20 0A 100 45A 20 12B 500 42B 100 10C 100 42C 20 8D 500 36D 100 0E 100 44E 20 10F 100 43F 20 8G 100 42G 20 8H 100 40H 20 52 + A 20 + 20 1002 + F 20 + 20 10015 + A 20 + 20 10015 + F 20 + 20 10022 + A 20 + 20 10022 + B 20 + 20 10022 + C 20 + 20 10022 + D 20 + 20 10054 + G 20 + 20 10054 + H 20 + 20 10059 + A 20 + 20 10059 + B 20 + 20 10059 + E 20 + 20 10059 + F 20 + 20 100105 + A 20 + 20 100105 + E 20 + 20 100110 + E 20 + 20 100110 + F 20 + 20 100117 + G 20 + 20 100117 + H 20 + 20 100141 + A 20 + 20 100141 + B 20 + 20 100181 + A 20 + 20 100181 + B 20 + 20 100181 + E 20 + 20 100181 + F 20 + 20 100______________________________________
As understood from the results shown in Table 12, the combined use of the N-phenylcarbamates (I) of the invention with benzimidazole thiophanate fungicides and/or cyclic imide fungicides show much more excellent preventive effect than their sole use.
EXPERIMENT 11
Preventive effect on gray mold of tomato (Botrytis cinerea):
A plastic pot of 90 ml volume was filled with sandy soil, and seeds of tomato (var: Fukuji No. 2) were sown therein. Cultivation was carried out in a greenhouse for 4 weeks. Onto the resulting seedlings at the 4-leaf stage, the test compound(s) formulated in emulsifiable concentrate or wettable powder and diluted with water were sprayed at a rate of 10 ml per pot. Then, the seedlings were inoculated with a mixed spore suspension of the drug-resistant and drug-sensitive strain of Botrytis cinerea by spraying and placed at 20.degree. C. in a room of high humidity for 5 days. The degree of damage was determined in the same manner as in Experiment 1, and the results are shown in Table 13.
TABLE 13______________________________________ Concentration of Prevention active ingredient valueCompound No. (ppm) (%)______________________________________ 2 100 42 2 20 0 15 100 32 15 20 0 22 100 38 22 20 0 54 100 40 54 20 0 59 100 32 59 20 0105 100 38105 20 0110 100 40110 20 0117 100 38117 20 0141 100 42141 20 0181 100 28181 20 0I 100 48I 20 22J 100 46J 20 18K 100 42K 20 15L 100 42L 20 122 + I 20 + 50 1002 + J 20 + 50 1002 + K 20 + 50 1002 + L 20 + 50 10015 + I 20 + 50 10015 + K 20 + 50 10022 + I 20 + 50 10022 + L 20 + 50 10054 + I 20 + 50 10054 + J 20 + 50 10059 + I 20 + 50 10059 + K 20 + 50 100105 + I 20 + 50 100105 + J 20 + 50 100110 + I 20 + 50 100110 + J 20 + 50 100117 + I 20 + 50 100117 + K 20 + 50 100141 + I 20 + 50 100141 + J 20 + 50 100181 + I 20 + 50 100181 + K 20 + 50 100______________________________________
As understood from the results shown in Table 13, the combined use of the N-phenylcarbamates (I) of the invention with benzimidazole thiphanate fungicides and/or cyclic imide fungicides show much more excellent preventive effect than their sole use.
Claims
  • 1. A N-phenylcarbamate compound selected from the group consisting of:
  • Isopropyl N-(3-methoxy-4-ethoxy-5-methoxycarbonylphenyl)-carbamate;
  • Isopropyl N-(3-methoxy-4-ethoxy-5-n-propylphenyl)-carbamate;
  • Isopropyl N-(3-ethyl-4-ethoxy-5-methoxymethylphenyl)-carbamate;
  • Isopropyl N-(3-vinyl-4-ethoxy-5-methoxymethylphenyl)-carbamate;
  • Isopropyl N-(3-bromo-4-ethoxy-5-methoxycarbonylphenyl)-carbamate;
  • Isopropyl N-[3-chloro-4-(2-chloroethoxy)-5-methoxymethylphenyl]carbamate;
  • Isopropyl N-[3-chloro-4-(2-bromoethoxy)-5-methoxymethylphenyl]carbamate;
  • Isopropyl N-(3-bromo-4-ethoxy-5-methoxymethylphenyl)-carbamate;
  • Isopropyl N-(3-methyl-4-ethoxy-5-methoxycarbonylphenyl)-carbamate;
  • Isopropyl N-(3-chloro-4-ethoxy-5-methoxycarbonylphenyl)-carbamate;
  • Isopropyl N-(3-methyl-4-ethoxy-5-propionylphenyl)-carbamate;
  • Isopropyl N-(3-fluoro-4,5-diethoxyphenyl)carbamate;
  • Isopropyl N-[3-chloro-4-(2,2,2-trifluoroethoxy)-5-methoxymethylphenyl]carbamate;
  • Isopropyl N-(3-methoxy-4-ethoxy-5-methoxymethylphenyl)-carbamate;
  • Isopropyl N-(3-chloro-4-allyloxy-5-methoxymethylphenyl)-carbamate;
  • Isopropyl N-(3-chloro-4-propargyloxy-5-methoxymethylphenyl)-carbamate; and
  • Isopropyl N-[3-chloro-4-(2-fluoroethoxy)-5-methoxymethylphenyl]-carbamate.
  • 2. The N-phenylcarbamate according to claim 1, which is Isopropyl N-(3-methoxy-4-ethoxy-5-methoxycarbonylphenyl)carbamate.
  • 3. The N-phenylcarbamate according to claim 1, which is Isopropyl N-(3-methoxy-4-ethoxy-5-n-propylphenyl)carbamate.
  • 4. The N-phenylcarbamate according to claim 1, which is Isopropyl N-(3-ethyl-4-ethoxy-5-methoxymethylphenyl)carbamate.
  • 5. The N-phenylcarbamate according to claim 1, which is Isopropyl N-(3-vinyl-4-ethoxy-5-methoxymethylphenyl)carbamate.
  • 6. The N-phenylcarbmate according to claim 1, which is Isopropyl N-(3-bromo-4-ethoxy-5-methoxycarbonylphenyl)carbamate.
  • 7. The N-phenylcarbamate according to claim 1, which is Isopropyl N-[3-chloro-4-(2-chloroethoxy)-5-methoxymethylphenyl]carbamate.
  • 8. The N-phenylcarbamate according to claim 1, which is Isopropyl N-[3-chloro-4-(2-bromoethoxy)-5-methoxymethylphenyl]carbamate.
  • 9. The N-phenylcarbamate according to claim 1, which is Isopropyl N-(3-bromo-4-ethoxy-5-methoxymethylphenyl)carbamate.
  • 10. The N-phenylcarbamate according to claim 1, which is Isopropyl N-(3-methyl-4-ethoxy-5-methoxycarbonylphenyl)carbamate.
  • 11. The N-phenylcarbamate according to claim 1, which is Isopropyl N-(3-chloro-4-ethoxy-5-methoxycarbonylphenyl)carbamate.
  • 12. The N-phenylcarbamate according to claim 1, which is Isopropyl N-(3-methyl-4-ethoxy-5-propionylphenyl)carbamate.
  • 13. The N-phenylcarbamate according to claim 1, which is Isopropyl N-(3-fluoro-4,5-diethoxyphenyl)carbamate.
  • 14. The N-phenylcarbamate according to claim 1, which is Isopropyl N-[3-chloro-4-(2,2,2-trifluoroethoxy)-5-methoxymethylphenyl]carbamate.
  • 15. The N-phenylcarbamate according to claim 1, which is Isopropyl N-(3-methoxy-4-ethoxy-5-methoxymethylphenyl)carbamate.
  • 16. The N-phenylcarbamate according to claim 1, which is Isopropyl N-(3-chloro-4-allyloxy-5-methoxymethylphenyl)carbamate.
  • 17. The N-phenylcarbamate according to claim 1, which is Isopropyl N-(3-chloro-4-propargyloxy-5-methoxymethylphenyl)carbamate.
  • 18. The N-phenylcarbamate according to claim 1, which is Isopropyl N-[3-chloro-4-(2-fluoroethoxy)-5-methoxymethylphenyl]carbamate.
  • 19. A fungicidal composition which comprises as an active ingredient a fungicidally effective amount of a compound of claim 1.
Priority Claims (3)
Number Date Country Kind
56-58303 Apr 1981 JPX
56-178509 Nov 1981 JPX
57-75768 May 1982 JPX
Parent Case Info

This is a continuation-in-part application of our copending application Ser. No. 367,404 filed on Apr. 12, 1982, now U.S. Pat. No. 4,482,546.

US Referenced Citations (5)
Number Name Date Kind
3592912 Ishiyama et al. Jul 1971
3933470 Cross et al. Jan 1976
3997325 Cross et al. Dec 1976
4482546 Takahashi et al. Nov 1984
4501756 Kato et al. Feb 1985
Foreign Referenced Citations (1)
Number Date Country
2921130 Dec 1980 DEX
Non-Patent Literature Citations (8)
Entry
Studies on Biological Activity of Cyclic Imide Compounds by Akira Fujinami et al, 1971, pp. 1707-1719.
Chemical Abstracts 64:17486h-17487b, 1966.
Chemical Abstracts 76:11016e, 1971.
Chemical Abstracts 84:121518t, 1976.
Chemical Abstracts 86:171071d, 1977.
Chemical Abstracts 88:100355e, 1978.
Chemical Abstracts 75:35491m, 1971.
Chemical Abstracts 76:11016e, 1972.
Continuation in Parts (1)
Number Date Country
Parent 367404 Apr 1982