United States Patent (19) 11 4,027,037 Siegle et al. (45) May 31, 1977

(54) N-SUBSTITUTED B-AMINOCROTONIC 57) ABSTRACT ACID ESTERS N-substituted (3-aminocrotonic acid esters of the for mula (75) Inventors: Peter Siegle, Cologne; Klaus Sasse, Schildgen; Peter Rössler, Cologne, all of Germany CH. COOR: (I) RC=CCN H (73) Assignee: Bayer Aktiengesellschaft, R11 Leverkusen, Germany in which (22 Filed: Mar. 12, 1975 R is hydrogen, or alkyl or alkenyl with up to 4 car bon atoms, (21) Appl. No.: 557,698 R’ is straight-chain or branched alkyl or alkenyl with up to 9 carbon atoms, optionally interrupted by O 30 Foreign Application Priority Data or S, and optionally substituted by halogen, phe Mar. 26, 1974 Germany ...... 2414456 noxy, dimethylamino, cyclic alkyl or alkenyl with up to 8 carbon atoms which are optionally substi (52) U.S. C...... 424/314; 260/239 BE; tuted by halogen, dimethylamino, or alkyl, alkoxy 260/239 BF; 260/247.2 B; 260/268 R; or alkylthio with up to 4 carbon atoms, phenyl 260/293.88; 260/326.43; 260/340.5; which is optionally substituted by halogen, dimeth 260/347.4; 260/468 G; 260/468 J; 260/470; ylamino, phenoxy, or alkyl, alkenyl, acyl, alkoxy, 260/471 A; 260/479 S; 260/481 R; 260/482 alkenoxy or alkynoxy containing up to 4 carbon R; 424/244; 424/2 48.52; 424/250; 424/267; atoms, or a 5- or 6-membered heterocyclic ring 424/274; 424/282; 424/285; 424/299; containing at least one O, S or N hetero-atom and 424/309; 424/248.55 optionally substituted by halogen, alkyl or alkoxy containing up to 4 carbon atoms or R is further (51 int. C.’...... C07C 101/28: A01N 9/20 more cyclic alkyl or alkenyl with up to 8 carbon 58) Field of Search ...... 260/482 R. 424/314 atoms optionally substituted by halogen, dimethyl amino, or alkyl, alkoxy or alkylthio with up to 4 (56) References Cited carbon atoms; phenyl optionally substituted by UNITED STATES PATENTS halogen, dimethylamino, phenoxy, or alkyl, alke 2,578,788 12/1951 Benneville ...... 260/482 R nyl, acyl, alkoxy, alkenoxy or alkynoxy containing 2,588,696 2/1952 Dickey ...... 424/314 up to 4 carbon atoms; or a 5- or 6-membered het 2,852,527 9/1958 Steck ...... 260/482 R erocyclic ring containing at least one O, S or N 2,976,285 3/1961 Gash ...... 260/471 A heteroatom and optionally substituted by halogen, 2,987,491 6/1961 Bader ...... 260/482 R or alkyl or alkoxy containing up to 4 carbon atoms; 3,265,698 8/1966 Allen et al...... 260/326.12 R O 3,420,827 1/1969 Leffingwell ...... 260/482 R R" and R together with the adjoining nitrogen atom FOREIGN PATENTS OR APPLICATIONS form a heterocyclic structure optionally substi tuted by lower alkyl with 1-4 carbon atoms and 1,120,802 12/1961 Germany optionally containing further heteroatoms in addi OTHER PUBLICATIONS tion to nitrogen, and R’ is straight-chain or branched alkyl, alkenyl or Sonnet, J.Agr. Food Chem., 2001), pp. 65-69, (1972). alkynyl each with up to 10 carbon atoms, or cyclic Nilies, J. Agr. Food. Chem., 21 (3), pp. 342-347, alkyl or alkenyl with up to 8 carbon atoms, option (1973). ally substituted by halogen, alkoxy or alkyl-thio Allen et al. II, J.A.C.S., 88, pp. 2536-2544, (1966). containing up to 4 carbon atoms, phenyl, 3,4- Allen et al., Beilstein, vol. 4, p. 467, (1922). methylenedioxyphenyl, cyclic alkyl or alkenyl with Allen et al., Beilstein, 1st Supp., vol. 4, pp. 889-890, up to 8 carbon atoms; phenyl optionally substi (1943). tuted by dioxymethylene or alkyl, alkenyl, alkynyl, Allen et al., Beilstein, 2nd Supp., vol. 4, pp. alkoxy, alkenoxy, alkynoxy or acyl containing up 1495-1496, (1963). to 4 carbon atoms; or a heterocyclic ring contain Arnold, Chem. Abst. 62:1 1672-3 (1965). ing up to 6 atoms of which at least one is O, N or Krasnaya, Chem. Abst. 78:71347q (1973). S, which ring is optionally bonded via alkyl con Wright, Chem. Abst., 81:22188s (1974). taining up to 4 carbon atoms, Primary Examiner-Lorraine A. Weinberger which inhibit the metamorphosis of arthropods. Assistant Examiner-Michael Shippen Attorney, Agent, or Firm-Burgess, Dinklage & Sprung 9 Claims, No Drawings 4,027,037 1 2 R is straight-chain or branched alkyl or alkenyl with N-SUBSTITUTED B-AMINOCROTONIC ACID up to 10 carbon atoms, optionally interrupted by O ESTERS or S, and optionally substituted by halogen, phe The present invention relates to and has for its ob noxy, dimethylamino, cyclic alkyl or alkenyl with jects the provision of particular new N-substituted g 5 up to 8 carbon atoms which are optionally substi aminocrotonic acid esters which inhibit the metamor tuted by halogen, dimethylamino, or alkyl, alkoxy phosis of arthropods, active compositions in the form. or alkylthio with up to 4 carbon atoms, phenyl of mixtures of such compounds with solid and liquid which is optionally substituted by halogen, dimeth dispersible carrier vehicles, and methods for producing ylamino, phenoxy, or alkyl, alkenyl, acyl, alkoxy, such compounds and for using such compounds in a 10 alkenoxy or alkynoxy containing up to 4 carbon new way especially for combating arthropods, e.g. in atoms, or a 5- or 6-membered heterocyclic ring sects and acarids, with other and further objects be containing at least one O, S or N hetero-atom and coming apparent from a study of the within specifica optionally substituted by halogen, alkyl or alkoxy tion and accompanying examples. containing up to 4 carbon atoms or cyclic alkyl or The inhibition of metamorphosis to which this speci 15 alkenyl with up to 8 carbon atoms optionally sub fication refers involves affecting the developmental stituted by halogen, dimethylamino, or alkyl, alk metabolism of arthropods, by, for example, preventing oxy or alkylthio with up to 4 carbon atoms; phenyl the ecdysis of larvae, the transformation to the pupa or optionally substituted by halogen, dimethylamino, to the imago, the deposition of eggs capable of develop phenoxy, or alkyl, alkenyl, acyl, alkoxy, alkenoxy ment, or the development of eggs which have been laid. 20 or alkynoxy containing up to 4 carbon atoms; or a This interrupts the generation cycle and reduces the 5- or 6-membered heterocyclic ring containing at population of the arthropods. This interference with least one O, S or N heteroatom and optionally development prevents the treated organisms from ma substituted by halogen, or alkyl or alkoxy contain turing and becoming capable of reproduction. ing up to 4 carbon atoms; or 25 R and R together with the adjoining nitrogen atom It is generally know that conventional animal bio form a heterocyclic structure optionally substituted cides, for example phosphoric acid esters, when used as by lower alkyl with 1-4 carbon atoms and option ingested poisons and contact poisons, kill both verte ally containing further heteroatoms in addition to brates and invertebrates through cholinesterase-inhibi nitrogen, and tion. Furthermore, it is already known that, in contrast 30 R is straight-chain or branched alkyl, alkenyl or to these conventional biocides which act as contact alkynyl each with up to 10 carbon atoms, or cyclic poisons or ingested poisons and kill the animals in a few alkyl or alkenyl with up to 8 carbon atoms, option hours, a juvenile hormone, or substances chemically ally substituted by halogen, alkoxy or alkyl-thio closely related to this hormone can be used to prevent containing up to 4 carbon atoms, phenyl, 3,4- the development of insects and spider mites, especially 35 methylenedioxyphenyl, cyclic alkyl or alkenyl with in the final phase of the development of pupae, or up to 8 carbon atoms; phenyl optionally substituted sexually mature imagos (J. J. Menn and M. Beroza: by dioxymethylene or alkyl, alkenyl, alkynyl, alk Insect Juvenilhormones, Chemistry & Action, Acade oxy, alkenoxy, alkynoxy or acyl containing up to 4 mie Press, New York 1972). carbon atoms; or a heterocyclic ring containing up For this reason, a large number of investigations have 40 to 6 atoms of which at least one is O, N or S, which concerned themselves with the chemical modification ring is optionally bonded via alkyl containing up to of the natural hormones. These investigations showed, 4 carbon atoms. in particular, that a fairly long unsaturated alkyl chain Preferably, R is hydrogen, alkyl or alkenyl with up to is responsible for good hormone activity (H.J. Zabiket 3 carbon atoms, especially methyl, ethyl or allyl; R is al., J.Agr. Food Chem. 21, 342 (1973)). 45 straight-chain or branched alkyl with up to 9 carbon Thus it has been found that g-aminocrotonic acid atoms which can optionally be substituted by norbor esters with citronellylamine or epoxycitronellylamine nyl, morpholine, chlorine, phenoxy, cyclohexyloxy, as the amino component are good juvenile hormone cyclohexy, cyclohexenyl, methylcyclohexenyl, furfuryl analogues (P. E. Sonnet et al., J.Agr. Food Chem. 20, or dimethylamine and can be interrupted one or more 65 (1972)). , , , , 50 times by O or S, or R’ is cyclopentyl, cyclohexyl, cy Further, it has been disclosed that g-aminocrotonic cloheptyl or cyclooctyl which are optionally substituted acid esters with long-chain amino groups and/or ester by methyl, isopropyl, methoxy or ethoxy, or allyl, or groups are good fungicides and acaricides (compare phenyl which is optionally substituted by chlorine, bro German Auslegeschrift (German Published Specifica mine, methyl, ethyl, ethoxy, allyloxy, propargyloxy, tion) 1,120,802). 55 dimethylamino, phenoxy or acetyl, or benzyl which is However, it is a disadvantage of these compounds optionally substituted by chlorine or ethyl; or RandR that the starting materials are too expensive, and that and the adjoining nitrogen atom form an optionally some of them can only be prepared with difficulty. methyl-substituted 5-, 6- or 7-membered heterocyclic The present invention provides g-aminocrotonic acid structure which can additionally contain N or O as a esters of the general formula 60 further heteroatom, especially morpholine, piperazine, piperidine, pyrrolidine or azepine; and R is straight CH COOR3 (I) chain or branched alkyl with 1 - 10 carbon atoms, Ricc=cC which can optionally be interrupted by O or S, lower -N H R1 alkenyl or alkynyl with up to 4 carbon atoms, phenyl, 65 acetylphenyl, propargyloxyphenyl, ethylphenyl, ethyl in which mercaptophenyl, isopropoxyphenyl, furfuryl, tetrahy R is hydrogen, or akyl or alkenyl with up to 4 carbon drofurfuryl, 34-yethylenedioxyphenyl or 3,4- atoms, methylenedioxybenzyl. 4,027,037 3 4 These compounds have been found to inhibit the development of arthropods, especially insects and spi CHFCH-CH, -NH, -- CH-CO-CH,-COOCHs der mites, above all during the ecdysis stages. The (a) (a) mode of action of the active compounds according to 5 the invention is novel and differs both from that of -Ge. CH DeC COOCH conventional insecticides and from that of chemosteril CHECH-CH-NH izing agents and of insect hormones. (1) H It is distinctly surprising that the compounds accord The reaction can be carried out according to the ingmorphosis-inhibiting to the invention, ofaction, the formula especially (I), exhibit since aonly meta a 10 conditions indicated in J. Am. Chem. Soc., Volume 88 very short-chain amine suffices to produce the full (1966) page 2,541. This process variant is preferred action. It follows from this that in contrast to previously because of the ready availability of the starting com known investigations, the length of the alkyl chain is of pounds. Amines of the formula (III) and acetoacetic subordinate importance, at least in the case of this acid esters of the formula (II) used therein are known particular system. Apparently, it is the 6-substituted 15 and can be prepared according to known processes. ester structure which is essential to pro Preferably, the amines indicated below are employed duce a good action. in carrying out the indicated process variants: ethyla A particular advantage of the active compounds ac mine, propylamine, isopropylamine, butylamine, cording to the invention is a pronounced genus-specific isobutylamine, tert-butylamine, pentylamine, 2,2- action. In this way it is possible to develop agents which 20 dimethylpropylamine, pentyl(2)-amine, hexylamine, are only active against certain pests. These active com 2-ethylhexylamine, heptylamine, octylamine, dimethyl pounds are thus of particular importance in developing amine, diethylamine, 2-chloroethylamine, 3-dime new methods, less detrimental to the environment, of combating pests. thylaminopropylamine, allylamine, 3-ethyl-pentene The compounds according to the invention have the 25 (3)-amine, diallylamine, 3-methoxypropylamine, 3 further advantage that they can be prepared simply and ethoxy-propylamine, 3-butoxy-propylamine, cyclohex inexpensively. ylamine, 3-ethylhexylamine, 4-ethylhexylamine, 3-iso The invention also provides a process for the produc propylhexylamine, 4-isopropylhexylamine, hexame tion of a 6-aminocrotonic acid ester according to the thyleneimine, 3-ethoxyhexylamine, 4-ethoxyhexyla 30 mine, 3-methylhexylamine, cyclopentylamine, 3 invention in which cyclohexoxypropylamine, octylamine, 4,7-dioxaoctyla a. an acetoacetic acid ester of the general formula mine, 4,7-dioxanonylamine, 4,7,9-trioxadodecylamine, CH-CO-CH-COOR (II) 4,7-dioxaundecylamine, 3-isopropoxypropylamine, 3 isobutoxypropylamine, 4-methoxypentylamine, 2(3- in which 35 methylpentoxy)-ethylamine, 2-(cyclohexen(3)-yl)- R has the abovementioned meaning, is reacted with ethylamine, 3-methylhexen(3)yl-methylamine, cy an amine of the general formula clohexen(3)yl-methylamine, 2-norbornylmethylamine, morpholine, furfurylamine, pyrrolidine, piperidine, R (III) N-methylpiperazine, N(3-aminopropyl)-morpholine, HN 40 n phenylamine, 4-chlorophenylamine, 4-bromophenyla R mine, 3-ethylphenylamine, 3-ethoxyphenylamine, 3 in which allyloxyphenylamine, 2-propargyloxyphenylamine, 4 R and R have the abovementioned meanings, op dimethylaminophenylamine, 4-phenoxyphenylamine, tionally in the presence of an organic diluent, or 45 4-acetylphenylamine, benzylamine, 4-chlorobenzyla b. an amine of the general formula (III) is reacted mine, 4-ethylbenzylamine, 2-ethylthioethylamine and with a tetrolic acid ester of the general formula 2-phenoxyethylamine. Preferably, the acetoacetic acid esters indicated CH-C = C-COOR (IV) below are used in carrying out the most important in which 50 process variant (a): acetoacetic acid methyl ester, ethyl R has the abovementioned meaning, optionally in ester, propyl ester, isopropyl ester, butyl ester, i-butyl the presence of a diluent, or ester, t-butyl ester, pentyl ester, i-pentyl ester, hexyl c. an amine of the general formula (III) is reacted ester, 1,3-dimethylbutyl ester, heptyl ester, octyl ester, with 6-chlorocrotonic acid ester of the general formula allyl ester, propargyl ester, 2-chloroethyl ester, 2-iso 55 propoxyethyl ester, cyclohexyl ester, benzyl ester, 4 acetyl-phenyl ester, 4-ethyl-phenyl ester, 3,4- CHs. COOR (V) methylenedioxyphenyl ester, furfuryl ester, tetrahydro 1.CRC N furfuryl ester, phenyl ester, p-chlorophenyl ester, o-iso C H propoxyphenyl ester, o-allyloxyphenyl ester, thio 60 phenyl ester, 4-ethylthiophenyl ester, 3,4-methylenedi in which R has the abovementioned meaning, oxybenzyl ester, cyclohexenyl ester, 2-ethylthioethyl optionally in the presence of a diluent and of an acid ester, 2-cyclohexylethyl ester, o-propargyloxyphenyl binding agent. ester or 4-allylphenyl ester. If allylamine and acetoacetic acid ethyl ester are used 65 If isobutylamine and tetrolic acid ethyl ester are used as starting materials, the course of the reaction of pro as starting materials, the course of the reaction in pro cess variant (a) can be represented by the following cess variant (b) can be represented by the following equation: equation: 4,027,037 S 6 acid ethyl ester, 6-(3-ethylphenylamino)-crotonic acid ethyl ester, g-(3-ethoxyphenylamino)-crotonic acid CH3N CH-CH-NH, + CH-C=C-COOC.H.- ethyl ester, 6-(3-allyloxyphenylamino)-crotonic acid CH (IIb) (IVa) ethyl ester, g-(2-propargyloxyphenylamino)-crotonic acid ethyl ester, 6-(4-dimethylaminophenylamino)- CH Yo-c1 COOCH crotonic acid ethyl ester, 3-(4-phenoxyphenylamino)- - SCH, / V crotonic acid ethyl ester, 3-(4-acetylphenylamino)- cH-CH, -NH H crotonic acid ethyl ester, 3-benzylaminocrotonic acid CH (2) ethyl ester, 6-(4-chlorobenzylamino)-crotonic acid The reaction can be carried out analogously to the 10 ethyl ester, 6-(4-ethylbenzylamino)-crotonic acid ethyl process indicated in Chemische Berichte, Volume 99, ester, 6-(2-ethylthioethylamino)-crotonic acid ethyl page 450. ester, 3-(2-phenoxyethylamino)-crotonic acid ethyl If allylamine and 6-chlorocrotonic acid ethyl ester ester, 6-diethylamino-crotonic acid ethyl ester, 6-dime are used as starting materials, the course of the reaction thylaminocrotonic acid ethyl ester and 6-allylamino of process variant (c) can be represented by the follow 15 crotonic acid 2-ethyl-mercaptoethyl ester. ing equation: The active compounds according to the invention, which have a low toxicity to warm-blooded animals and CHs. low phytotoxicity, surprisingly exhibit a specific meta CHFCH-CH-NH, +C=CH-COOCH, morphosis-inhibiting action. This action manifests itself (IIIa) Cl (Va) 20 during the ecdysis which is typical of arthropods only CH 1. COOCH2 is and in some cases the action also continues over sev -G) C=C- eral stages of development and first comes into play CH,FCH-CH-NH H during the transformation to the chrysalis or during (l) slipping. The active compounds can, therefore, be used The invention of course encompasses both cis- and 25 very successfully for combating harmful arthropods, trans-isomers of the compounds of formula (I). In prac especially harmful sucking and biting insects and spider tice, the abovementioned process for the preparation mites. They may, therefore, be used in plant protection of these compounds generally result in a predominant and the protection of stored products, in the hygiene production of the trans-isomers. field and for destroying insects in permanently or tem If desired a diluent may be used in the processes 30 porarily stagnant . They furthermore have a de indicated. All inert organic solvents can be used for this gree of fungicidal and plant growth-regulating activity. purpose. In the case of variant (a), a solvent together The arthropods include, for example, orders and with which the of reaction can be distilled off species such as the Entomostraca, for example Artemia azeotropically, such as or methylene chloride, salina; the Cladocera, for example species of Daphnia, is preferred. and the Copepoda, for example Cyclops vernalis; and In the case of process variant (c), an excess of amine the Malacostraca, amongst which are counted the is preferably employed as an acid-binding agent. Isopoda including Oniscus asellus, Armadilidium vul In other respects, the starting compounds are gener gare and the genus Gammaridae. The Diplopoda in ally employed in molar amounts when carrying out the clude species such as Glomeris pustulata and Blaniulus process variants according to the invention. An excess 40 guttulatus; the Chilopoda, including Scutigera species, of one or other starting component is not detrimental Lithobius forficatus and Geophilus carpophagus, and the but also produces no significant increase in the yield of Symphyla, including Scutigerella immaculata. The compounds according to the invention. The reaction temperatures can be varied over a sub Arachnida include pests and venomous animals such as stantial range; in general, the reaction is carried out at 45 Chelifer cancroides, Buthus occitanus, Latrodectus nac 0° to 100°C, preferably 20 to 50° C. tans and the genus Mygale. The harmful Acarina in The following may be mentioned individually as new clude species such as Dermanyssus gallinae and plant active compounds of formula (I): 3-allylaminocrotonic pests such as Eriophyes ribis, Phylocoptruta oleivora, acid 4-acetylphenyl ester, 6-allylaminocrotonic acid Tarsonemus pallidus, Panonychus citri and ulmi, Tet 4-ethylphenyl ester, g-allylaminocrotonic acid 3,4- 50 ranychus urticae, Tetranychus telarius, Tetranychus methylenedioxy-phenyl ester, 6-furfurylaminocrotonic tumidus and the Ixodoidea such as Dermacentor spe acid propyl ester, 6-morpholinocrotonic acid propyl cies, and Ornithodorus moubata. The Hexpods include ester, 6-allylaminocrotonic acid furfuryl ester, 6 the Thysanura such as Lepisma saccharina; the Collem allylaminocrotonic acid tetrahydrofurfuryl ester, 3 bola such as Onychiurus species; the Plecoptera; the allylaminocrotonic acid 4-propargyloxyphenyl ester, 55 Orthoptera such as Blatta orientalis, Periplaneta ameri g-allylaminocrotonic acid 4-ethylmercaptophenyl es cana and Acheta domesticus, and agricultural pests such ter, 6-allylaminocrotonic acid thiophenyl ester, 6 as Locusta migratoria, Melanoplus differentialis and allylaminocrotonic acid 3,4-methylenedioxybenzyl es Schistocera gregaria, and the Dermaptera, for example ter, 6-allylaminocrotonic acid cyclohexyl ester, g Forficula auricularia. Also to be mentioned are the allylaminocrotonic acid benzyl ester, 6-allylaminocro 60 harmful insects of the Isoptera such as Reticulitermes tonic acid o-isopropoxyphenyl ester, 6-anilinocrotonic species; the Mallophaga, such as Trichodectidae spe acid ethyl ester, 6-diallylaminocrotonic acid ethyl es cies; the Anoplura such as Pediculus humanus corporis, ter, (3-(2-chloroethyl)-aminocrotonic acid ethyl ester, Phylloxera vastatrix and Pemphigus species; and the B-pyrrolidinocrotonic acid ethyl ester, g-piperidinocro Thysanoptera such as Hercinothrips femoralis and tonic acid ethyl ester, 6-(N-methyl-piperazino)-cro 65 Thrips tabaci. The harmful Heteroptera include, for tonic acid ethyl ester, 6-(N-(3-aminopropyl)-mor example, Cimex lectularius, Rhodnius prolixus, Triat pholino)-crotonic acid ethyl ester, 6-(4-chloroanilino)- oma infestans and plant pests such as Eurygaster spe crotonic acid ethyl ester, 6-(4-bromoanilino)-crotonic cies, Dysdercus intermedius and Piesma quadrata. 4,027,037 7 8 Amongst the Homoptera are included species such as chloroethylenes, etc.), alcohols (e.g. methanol, etha Aleurodes brassicae, Bemisia tabaci, Dialeurodes citri, nol, propanol, butanol, glycol, etc.) as well as ethers Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ri and esters thereof (e.g. glycol monomethyl ether, etc.), bis, Doralis fabae and pomi, Myzus persicae, Phorodon amines (e.g. ethanolamine, etc.), amides (e.g. dimethyl humuli and Rhopalosiphum padi. The Cicadellidae in formamide, etc.), sulfoxides (e.g. , clude species such as Euscelis bilobatus, Lecanium etc.), acetonitrile, ketones (e.g. acetone, methyl ethyl corni, Saissetia oleae, Laodelphax striatellus, Aonidiella ketone methyl isobutyl ketone, cyclohexanone, etc.), auranti, Pseudococcus species and species of Psylla. and/or water; as well as inert dispersible finely divided The harmful Lepidoptera include species such as Pec solid carriers, such as ground natural minerals (e.g. tinophora gossypiella, Bupalus piniarius, Cheimatobia 10 kaolins, clays, alumina, silica, chalk, i.e. calcium car brumata, Lithocolletis blancardella, Hyponomeuta bonate, talc, attapulgite, montmorillonite, kieselguhr, padella, Plutella maculipennis, Malacosoma neustria, etc.) and ground synthetic minerals (e.g. highly dis Euproctis chrysorrhoea, Lymantria species, Bucculatrix persed silicic acid, silicates, e.g. alkali silicates, etc.); thurberiella, Phyllocnistis citrella, Agrotis species, whereas the following may be chiefly considered for Euxoa species, Feltia species, Earias insulana, Heliothis 15 use as conventional carrier vehicle assistants, e.g. sur species, Laphygma exigua, Mamestra brassicae, Panolis face-active agents, for this purpose: emulsifying agents, flammae, Prodenia litura, Spodoptera species, Trichu such as non-ionic and/or anionic emulsifying agents plusia ni, Carpocapsa pomonella, Pieris species, Chilo (e.g. polyethylene oxide esters of fatty acids polyethy species, Pyraustra nubilalis, Ephestia kuhniella, Galleria lene oxide ethers of fatty alcohols, alkyl sulfates, alkyl melonella, Capua reticulana, Choristoneura 20 sulfonates, aryl sulfonates, albumin hydrolyzates, etc., fumiferana, Clysia ambiguella and Tortrix viridana. The and especially alkyl arylpolyglycol ethers, magnesium order of the Coleoptera includes domestic pests, pests stearate, sodium oleate, etc.); and/or dispersing agents, of stored products and plant pests such as Acanthosce such as lignin, sulfite waste liquors, methyl cellulose, lides obtectus, Oryzaephilus surinamensis, Dermestes etc. peruvianus, Trogoderma granarium, Sitophilus 25 Such active compounds may be employed alone or in granarius, Tribolium confusum, Tenebrio species, Lep the form of mixtures with one another and/or with such tinotarsus decenlineata, Phaedon cochleariae, Epilachna solid and/or liquid dispersible carrier vehicles and/or varivestis, Anthomomus species, Anthremus verbasci, with other known compatible active agents, especially Diabrotica species, Agriotis species, and Melolontha plant protection agents, such as nematocides, insecti vulgaris. Amongst the Hymenoptera are included or 30 cides, acaricides, fungicides, bactericides, rodenticides, ganisms such as Diprion species and Haplocampa spe herbicides, fertilizers, growth-regulating agents, etc., if cies. The Diptera include harmful species such as Os desired, or in the form of particular dosage prepara cinella frit, Drosophila melanogaster, Pegomyia hyos tions for specific application made therefrom, such as cyami, Ceratitis capitata, Dacus oleae, Phorbia species, solutions, emulsions, suspensions, powders pastes, and Caliphora erythrocephala, Aedes aegypti, Anopheles 35 granules which are thus ready for use. stephensi, Stomoxys calcitrans, Tabanus bovinus, Phle Other known active compounds include dimethylcar botomus species and the Simuliidae. The Siphonapetra bamates such as 5,5-dimethyl-4,5-dihydroresorcinol include species such as Xenopsylla cheopis. dimethylcarbamate, 1-isopropyl-3-methyl-5-pyrazolyl The active compounds according to the instant in dimethylcarbamate, 1-phenyl-3-methyl-5-pyrazolyl vention can be utilized, if desired, in the form of the 40 dimethylcarbamate, 2-dimethylcarbamyl-3-methyl-5- usual formulations or compositions with conventional pyrazolyl-dimethylcarbamate, 1 (2-alkoxycarbonyle inert (i.e. plant compatible or herbicidally inert) pesti thyl)-3-methylpyrozalyl 5-dimethylcarbamate, 2-n-pro cide diluents or extenders, i.e. diluents, carriers or pyl-4-methyl-6-pyrimidyl-dimethylcarbamate, as well extenders of the type usable in conventional pesticide as methylcarbamates of phenols such as 3,4-dimethyl formulations or compositions, e.g. conventional pesti 45 6-chlorophenyl methylcarbamate, 3-methyl-5-iso cide dispersible carrier vehicles such as gases, solu propylphenyl methylcarbamate, 2-(1-methylpropyl)- tions, emulsions, suspensions, emulsifiable concen phenyl methylcarbamate, m-tolyl N-methylcarbamate, trates, spray powders, pastes, soluble powders, dusting 3,4,5-trimethylphenyl methylcarbamate, 2-chlorophe agents, granules, etc. These are prepared in known nyl methylcarbamate, 3,4-dimethyl phenyl N-methyl manner, for instance by extending the active com 50 carbamate, 3,5-di-tert-butylphenyl methylcarbamate, pounds with conventional pesticide dispersible liquid 2-(1,3-dioxolan-2-yl)-phenyl methylcarbamate, 3 diluent carriers and/or dispersible solid carriers option methyl-4-dimethylaminophenyl N-methylcarbamate, ally with the use of carrier vehicle assistants, e.g. con 3,5-dimethyl-4-diallylaminophenyl methylcarbamate, ventional pesticide surface-active agents, including 3,5-dimethyl-4-dimethylaminophenyl methylcarba emulsifying agents and/or dispersing agents, whereby, 55 mate, 3(N,N-dimethylaminomethyleneimino)-phenyl for example, in the case where water is used as diluent, methylcarbamate, dimethylaminomethyleneimino)- organic solvents may be added as auxiliary solvents. phenyl-methylcarbamate, 2-isopropoxyphenyl methyl The following may be chiefly considered for use as carbamate, 3,5-dimethyl-4-methylmercaptophenyl N conventional carrier vehicles for this purpose: aerosol methylcarbamate, as well as carbamates of polynuclear propellants which are gaseous at normal temperatures 60 compounds such as 1-naphthyl methylcarbamate, 2,2- and pressures, such as freon; inert dispersible liquid dimethyl-2,3-dihydro-7-benzofuranyl methylcarba diluent carriers, including inert organic solvents, such mate and 2-methyl-2,3-dihydro-7-benzofuranyl me as aromatic hydrocarbons (e.g. benzene, toluene, xy thylcarbamate, as well as methylcarbamates of oximes lene, alkyl naphthalenes, etc.), halogenated, especially such as 1-methylthio-acetaldehyde-0-(methylcar chlorinated, aromatic hydrocarbons (e.g. chloroben 65 bamoyl)-oxime and 2-methyl-2(methylthio)-pro Zenes, etc.) cycloalkanes (e.g. cyclohexane, etc.), par pionaldehyde-0-(methylcarbamoyl)-oxime, and also affins (e.g. petroleum or mineral oil fractions), chlori phosphoric acid esters such as 4,4'-bis-(0,0-dime nated aliphatic hydrocarbons (e.g. methylene chloride, thylthionophosphoryloxphenyl)-sulfide, 0-ethyl-0- 4,027,037 9. 10 (2,4,5-trichlorophenyl)-ethanethiophosphonic acid the present invention contemplates over-all composi ester, 0.0-dimethyl-0-4(4'-chlorophenylazo)-phenyl)- tions which comprise mixtures of a conventional dis thiophosphoric acid ester, 0,0-diethyl-0-(3-chloro-4- persible carrier vehicle such as (1) a dispersible inert methyl-7-coumarinyl)-thiophosphoric acid-ester, 0.0- finely divided carrier solid, and/or (2) a dispersible diethyl-0-quinoxalyl(2)-thionophosphoric acid ester, carrier liquid such as an inert organic solvent and/or 0,0-dimethyl-O-(3-chloro-4-nitrophenyl)-thionophos water preferably including a surface-active effective phoric acid ester, S-(0,0-dimethylthionophosphoryl)-1-. amount of a carrier vehicle assistant, e.g. a surface-ac phenyl-1-mercaptoacetic acid ethyl ester, 0,0-dimeth tive agent, such as an emulsifying agent and/or a dis yl-(1-hydroxy-2,2,2-trichloroethyl)-phosphonic acid persing agent, and an amount of the active compound ester, 0.0-diethyl-S-(2-ethylmercaptoethyl)-dithio 10 which is effective for the purpose in question and which phosphoric acid ester, 0,0-diethyl-S-(ethylsulfinyle is generally between about 0.0001-95%, and prefer thyl)-dithiophosphoric acid ester, 0,0-diethyl-0-3,5,6- ably 0.01-95%, by weight of the mixture. trichloropyridyl-(2)-thiophosphoric acid ester, 0.0- The active compounds can also be used in accor dimethyl-S-(methylcarbamoylmethyl)-thiophosphoric dance with the well known ultra-low-volume process acid ester, 0,0-dimethyl-0-(3-methyl-4-nitrophenyl)- 15 with good success, i.e. by applying such compound if thiophosphoric acid ester, 0,0-dimethyl-S-(4-oxoben normally a liquid, or by applying a liquid composition zotriazine-3-methyl)-dithiophosphoric acid ester, 0 containing the same, via very effective atomizing ethyl-S,S-diphenyldithiophosphoric acid ester, 0,0- equipment, infinely divided form, e.g. average particle dimethyl-S-phthalimidomethyl-dithiophosphoric acid diameter of from 50-100 microns, or even less, i.e. mist ester, 0,0-dimethyl-S-(p-chlorophenylmercaptome 20 form, for example by airplane crop spraying tech thyl)-dithiophosphoric acid ester, 0,0-dimethyl-O-(2- niques. Only up to at most about a few liters/hectare ethylmercaptoethyl)-thiolphosphoric acid ester, 0.0- are needed, and often amounts only up to about 15 to diethyl-S-benzyl-thiolphosphoric acid ester, 0-phenyl 1000 g/hectare, preferably 40 to 600 g/hectare, are N,N'-dimethylphosphoric acid diamide,0,0,0',0'-tetra sufficient. In this process it is possible to use highly ethyl-S,S'-methylene-bis-dithiophosphoric acid ester, 25 concentrated liquid compositions with said liquid car tetra-n-propyldiethionopyrophosphoric acid ester, 0.0- rier vehicles containing from about 20 to about 95% by diethyl-0-3-methylpyrazolyl(5)-phosphoric acid es weight of the active compound or even the 100% active ter, 0,0-dimethyl-S-(N-methylcarbamoylmethyl)-dithi substance alone, e.g. about 20-100% by weight of the ophosphoric acid ester, 2-methoxy-4-H-1,3,2-benzodi active compound. oxaphosphorane-2-thione, 0,0-dimethyl-S-5-methoxy 30 Furthermore, the present invention contemplates 1,3,4-thiadiazol-2-(3-H)-on-3-yl-methyl)-dithiophos methods of inhibiting metamorphosis. of arthropods phoric acid ester, 0,0-diethyl-O-(p-methyl sulfinyl which comprises applying to at least one of correspond phenyl)-thiophosphoric acid ester, 0,0-diethyl-S- ingly (a) such arthropods and (b) the corresponding (ethylmercaptomethyl)-dithiophosphoric acid ester, habitat thereof, i.e. the locus to be protected, e.g. to a 0,0-dimethyl-S-(2-(1-methylcarbamoylethylmercap 35 growing crop, to an area where a crop is to be grown or to)-ethyl-dithiophosphoric acid ester, 0-methyl-0- to a domestic animal, a correspondingly inhibitory (2,4-dichlorophenyl)-N-isopropylthiophosphoric acid amount of the particular active compound of the inven amide, and also the naturally occurring pyrethrins such tion alone or together with a carrier vehicle as noted as chrysanthemum-acid, pyrethric acid and pyrethroids above. The instant formulations or compositions are such as Pyrethrum, Alethrin, Cyclethrin, Barthrin, 40 applied in the usual manner, for instance by spraying, Dimethrin, Phthalithrin and Japothrin, and also rote atomizing, vaporizing, scattering, dusting, watering, noids, as well as alkaloids, insecticidal proteins such as squirting, sprinkling, pouring, fumigating, and the like. microbial insecticides, fluoroacetic acid derivatives, It will be realized, of course, that the concentration thiocyanic acid esters, such as g-butoxyethoxyethyl of the particular active compound utilized in admixture thiocyanate, diarylmethanes and diarylcarbinols such 45 with the carrier vehicle will depend upon the intended as 1,1-bis-(4-chlorophenyl)-2,2,2-trichloroethane and application. Therefore, in special cases it is possible to 1,1-bis-(4-chlorophenyl)-, nitrophenol deriva go above or below the aforementioned concentration tives such as 4,6-dinitro-2-cyclohexylphenol, 4,6-dini ranges. tro-2-cyclohexylphenol dicyclohexylamine salt, 4 The unexpected superiority and outstanding activity nitro-2,6-di-tert-butylphenol and 4,6-dinitro-2-(1- 50 of the particular new compounds of the present inven methylheptyl)-phenylcrotonate, diaryl thioethers and tion are illustrated, without limitation, by the following diarylsulfones, such as 2,4,5,4'-tetrachlorodiphenyl examples. sulfide, diphenylsulfone, aryl-benzyl-thioethers, -sulf The experiments described in Examples 1 to 3 illus oxides and -sulfones and aryl-alkyl-thioethers, diary trate the arthropod metamorphosis-inhibiting action of loxy- and diarylmercapto-alkanes, arylhydrazine com 55 compounds according to the invention, without imply pounds and arylazo compounds, such as azobenzene, ing any restriction with regard to the breadth of action and amidines, such as N-(2-methyl-4-chlorophenyl)- of these compounds. In these experiments the morpho N',N'-dimethylformamidine. . . . - logical changes, such as half-formed pupae, incom As concerns commercially marketed preparations, pletely slipped larvae or caterpillars, defective wings, these generally contemplate carrier composition mix 60 pupal cuticula in the case of imagos, and mortality, are tures in which the active compound is present in an assessed over the entire specified development of the amount substantially between about 0.1-95% by test animals. The sum of the morphological malforma weight, and preferably 0.5-90% by weight, of the mix tions and mortality during development is quoted as a ture, whereas carrier composition mixtures suitable for value index, and the indexes have the following mean direct application or field application generally con 65 Ings. : . . .'s. template those in which the active compound is present 1 = 90 - 100% malformation or mortality in an amount substantially between about 0.0001-10%, 2 = 80 - 89% malformation or mortality preferably 0.01-1%, by weight of the mixture. Thus, 3 = 70 - 79% malformation or mortality 4,027,037 11 12 4 = 60 - 69% malformation or mortality Feed: 1 cm thick disc, of 3 cm diameter, of partially 5 = 50 - 59% malformation or mortality air-dried synthetic feed of shredded beans, yeast, vita 6 = 40 - 49% malformation or mortality min mixture, powdered leaf, agar and preservative 7 = 30-39% malformation or mortality Solvent: 10 parts by weight of acetone 8 = 10 - 29% malformation or mortality Emulsifier: 1 part by weight of polyoxyethylene-(20) 9 = 0 - 9% malformation or mortality sorbitan monolaurate To produce a suitable preparation of active com EXAMPLE 1. pound, 2 parts by weight of active compound were Metamorphosis-inhibiting action/ingestion test mixed with the stated amount of solvent and emulsifier Test insects: Plutella maculipennis (caterpillars in the 10 and sufficient water to give a 1% strength mixture 4th stage of development) - 20 specimens Phaedon which was diluted with water to the desired concentra cochleariae (larvae) - 20 specimens tion. Feed plants: Cabbage plants (Brassica oleracea) One test insect per disc was placed on a feed disc Solvent: 10 parts by weight of acetone which had been moistened with 1.5 ml of active com Emulsifier: 1 part by weight of polyoxyethylene sor 15 pound solution of the stated concentration and was bitan monolaurate observed until the imago slipped. To produce a suitable preparation of active com As a control, one test insect per disc was placed on a pound, 2 parts by weight of active compound were feed disc moistened with 1.5 ml of solvent and emulsi mixed with the stated amount of solvent and emulsifier fier of the corresponding concentration and observed and sufficient water to produce a 1% strength mixture 20 until the imago slipped. The results can be seen from which was diluted with water to the desired concentra the table which follows: tion. Table 2 The test insects were fed with leaves of the feed Metamorphosis-inhibiting action/Laphygma test plants, which carried a uniform sprayed coating of the 25 Test insects: Laphygma active compound mixture of the stated concentration, Active compound concentration 0.1% 0.001% until the imago developed. Control 9 9 As a control, specimens were fed with leaves which Active Compound No. CHa-COOCHs 1 4. had only been treated with solvent and emulsifier of the CFCS stated concentrations. The results can be seen from the 30 CH=CH-CH-NH H table which follows: (1) Table CH chcooch. 2 2 Metamorphosis-inhibiting action/ingestion test CH-H NH -N Pha CH (5) H COOCH 2 6 Test insects: edon Plutela 35 CHis C s 2 is Active compound concentration: 0.01% 0.01%, 0.001% N-(CH,)-N H Control 9 9 9 CH H (7) Active Compound No. CH COOCH 2 4. CH,FCH-CH,- CHO-(CH), -NH1. TH (8) CH Do=C3COOCH 5 1. 1 40 CH COOCH -NH (1) H -- CH-N-CH COOCH 8 2 2 (9) CH H (2) CH CH-cooch l 2 45 CH ~9- o H CH-HCH ch-cooch.NH -N 6 2 2 (10) CH (5) CH COOCH 5 2 2 EXAMPLE 3 CH D-CH-NH s H CH (6) 50 Metamorphosis-inhibiting action/Aedes aegypti test CH COOCH 8 CHs. Test insects: Aedes aegypti (larvae) N-(CH,)-N H CH H (7) Solvent: 10 parts by weight of acetone CH COOCH 6 1 Emulsifier: 1 part by weight of polyoxyethylene-(20) sorbitan monolaurate CHO-(CH, -NH 1TYH 55 To produce a suitable preparation of active com (8) pound, 2 parts by weight of active compound were Sl-cooch.1 TN 8 1 mixed with the stated amount of solvent and emulsifier (9) and sufficient water to produce a mixture containing CH CH COOCH 6 60 100 ppm, which was diluted with water to the desired concentration. ch, U)-N'- The test insects were dipped in 90 ml of these active (10) compound solutions and observed until the imago slipped. As a control, test insects were introduced into 65 a mixture of solvent, emulsifier and water of the stated EXAMPLE 2 concentration and observed until the imago slipped. Metamorphosis-inhibiting action/Laphygma test The results can be seen from the table which follows: Test insects: Laphygma exigua (caterpillars) 4,027,037 Table 4 EXAMPLE 4 Metamorphosis-inhibiting action/Aedes aegypt,test Test insects; Aedes aegypti Active compound concentration 1 ppm 0.1 ppm "Sc=c COOCHs (1) Control-- 9 - 9 - 5 CH,-CH-CH-NH1 YH Active Compound No. CH >= COOCH 3. 5 6 20.1 g (0.35 mole) of allylamine were added drop NH H (4) wise to 52 g (0.4 mole) of acetoacetic acid ethyl ester CH COOCH 10 while stirring and cooling. The temperature was not > =< permitted to exceed 45 C. The reaction mixture was (9) then stirred for a further 4 hours at 45°C and subjected H CH COOCH to vacuum distillation. Boiling point s = 125-127 C, CH >< 2. Rs yield: 41 g (70% of theory). CH NH H (10) The following were prepared analogously:

CH CH COOCH boiling point NND-C, 0.15 = 67 C dH, H (2) CH COOCH boiling CHs. 1n 1a >=< pointo. r -N N H 124°C CH H (3) CHs. COOCH boiling >e-C pointo a F (E)-NH H (4) 115-17 C CHCH COOCH boiling 3. >=< points F CH NH H 120° C CH (5) CH COOCH boiling ">-ch -N h points == CH 2 (6) 120-130' C

CH ra CH ms cooch, boilingpointos = N-(CH,)-N H 125-127 C CH H (7) CH . COOCH boiling mo pointo F CHO-(CH-NH H 120°C (8) CH boiling ) cooch, pointo.6 = N H 5 C (9)

CH CH COOCH boiling 3. D=< point = CH NH H 130°C (10) boiling CH cooch, CSCH points = CHFCH-CH, -NH H 100°C (11) CH COOCH boiling

CH-CH-NH (12) panas80°C -

CH COOCH boiling ch-cha-ch-Ns-(CH,)-CH-NH H pointoss70-72°C (13) CH CH CH COOCH boiling D=< point = CH CH-NH H 72 C CH (14) 4,027,037 16 -continued CH COOCHs boiling >=< pointo. = NH H 30-40°C CHs (15) W CH Mixture of 3,4-isopropyl compounds CH COOC.H. boiling erre point. F CH-(CH), NH H 100°C (16) CH COOCHs boiling >=< pointo F CH-O NH H 142°C (17) CH COOCH's boiling >=< point. F NH H 104°C (8) CH boiling CH COOCH point. F D-C 10-115 C NH H (9) CH COOCH boiling DeC pointoss (E)-o-(CH-NH H (20) 158-160 C CH COOCH boiling >=< pointo see NH H 120-122C

CH s boiling N ) - N.coo-ch-c=ch pointo40-145 F C (22) CH COOCH boiling P pointoos F CH-O-(CH)-o-(CH,) NH H 138 C (23) CH COOCHs. boiling d pointos F CH-O-(CH,)-O-(CH,) NH H 120°C (24) CH, COOCHs boiling pointos = CH-O-(CH,)-o-(CH,), O-(CH,) NH H 190° C. (25) CH COOCH subjected as to CH-O-(CH,)-O-(CH,) NH H incipient (26) dis tilation CH COOCH boiling CHs. >=< pointlo,as is CH-O-(CH, -NH H 106-08 C CH (27) CH COOCH boiling CHs. >=< . point. F ccH-CH-O-(CH,), -NH H 124-126 C CH (28) CH COOCH boiling >=< is pointo F CH, -CH, -NH H 130°C (29) CH COOCHs boiling pointo F CHis CH-NH H 134C (30) CH COOCHs. boiling ams pointos F CH-NH H 120-140°C (31) * 4,027,037 s: 17 18 -continued CH COOCH boiling pointos = CH-CH-(CH)-NH H 110-115 C (32) CHO CHs CH COOCH boiling pointo CH-CHEC-CH, -CH-NH H 16-18 C (33) CHs CH COOCH boiling. . pointoz - CH-CH-CH, -CH,-o-CH-CH-NH 13438 C (34) CH COOCH boiling OL CH, -NH >=< H points130-135°C (35) CH, cooch, sesCHFCH point.boiling F CHECH-CH-NH H 99-02 C (36) CH COOCH boiling >=< s '...pointo F CHCH-CH-NH H (37) 124-127C CHs boiling CH COOCH-CH-OCH pointo F >=< we YoH, 100-104°C CHECH-CH-NH H - . (38) boiling CH cooch), CH point F CHECH-CH-NH H 130-134C (39) boiling C COOCH-CH-CH points F >-C ch, 95-97°C CHFCH-CH-NH H CH, (40) CH COOC(CH) boiling C S3 pointos F CHECH-CH, -NH H (41) 75-80°C

CH COOCH, sp CH-CH,v as boilingpoint F CHECH-CH-NH H 91-94°C (42) melting CH, coo-) pointint. 50C - CHECH-CH-NH H (43) CHs boiling CH CooCH-CHN points. CH OO-105 C CH=CH-CH, -NH H (44) CH COO-CHw boilingpointo F (CHs)N H 45 160-65°C (45) 16.3 g of 6-chlorocrotonic acid propyl ester were EXAMPLE 5 dissolved in 100 ml of toluene. 10.3 g of allylamine 60 were then: slowly added dropwise. The mixture was The illustrated compound then stirred for a further 2 hours at 40° C and the hy drochloride which had precipitated was filtered off. CH COOCH-CH-CH The filtrate was subjected to distillation. The desired CHECH-CH, -NH H compound was obtained at boiling point = 95°-100 (42) C. 65 Other compounds which can be similarly prepared was also prepared as follows: include: w

4,027,037 22 -continued C

CH

CH COOCH

ch=c-ch-o-)-N- (64) CH COOCH

()-o-)-Nish (65) CH, cooch, chco-)-NH H (66) Cl CH D=< COOCHs. CHs CH-NH H (67) Chis COOCH

H (68) CH COOCH CH, N, N H V/ (69) COOCH

(70) 3. A compound according to claim 1 wherein such compound is g-(2-methoxyethylamino)-crotonic acid ethyl ester of the formula 40 It will be appreciated that the instant specification CH COOCH and examples are set forth by way of illustration and not limitation, and that various modifications and CHO-(CH, -NH H changes may be made without departing from the spirit and scope of the present invention. 45 4. An arthropod metamorphosis inhibiting composi What is claimed is: tion containing as active ingredient a metamorphosis 1. A compound selected from the group consisting of inhibitory amount of a compound according to claim 1 g-allylaminocrotonic acid ethyl ester of the formula in admixture with a diluent. 5. A method for combating arthropod pests which 50 comprises applying to the pests or a habitat thereof a CHs. COOC.H. metamorphosis inhibitory amount of a compound se lected from the group consisting of 3-allylaminocro tonic acid ethyl ester, 6-(2-methoxyethylamino)-cro and 6-(2-methoxyethylamino)-crotonic acid ethyl ester tonic acid ethyl ester, 3-(2-ethylhexylamino)-crotonic of the formula 55 acid ethyl ester, or 6-(tert-butylamino)-crotonic acid ethyl ester. CH COOCH 6. The method according to claim 5 wherein such compound is 6-allylaminocrotonic acid ethyl ester. 7. The method according to claim 5 wherein such CHO-(CH)-NH H 60 compound is 6-(2-methoxyethylamino)-crotonic acid ethyl ester. 2. A compound according to claim 1 wherein such 8. The method according to claim 5 wherein such compound is g-allylaminocrotonic acid ethyl ester of compound is g-(2-ethylhexylamino)-crotonic acid the formula ethyl ester. 65 9. The method according to claim 5 wherein such CHs. COOC.H. compound is g-(tert-butylamino)-crotonic acid ethyl CFC N CHFCH-CH, -NH H ester. ck k k UNITED STATES PATENT AND TRADEMARK OFFICE CERTIFICATE OF CORRECTION () PATENT NO. 4,027,037 Page 1 of 2 DATED May 31, 1977 NVENTOR(S) : Peter Siegle, et al. It is Certified that error appears in the above-identified patent and that said Letters Patent () are hereby Corrected as shown below: Col. 2, line 48 cancel 'cyclohexy' and substitute - c. cyclohexyl - - Col. 5, line 2 cancel "(i.Ib)" and substitute -- (IIIb) - Col. 6, line 42 cancel 'carpophagus' and substitute -- carpaophagus - - Col. 7, line 19 cancel "Kuhniella" and substitute -- Kuhniella - - Col. 8, line 34 after 'powders' insert - - , -- Col. 8, line 42 cancel "pyrozalyl" and substitute -- pyrazolyl -- Col. 8, lines 56-57 delete 'dimethyl... carbamate" Col. 8, line 68 cancel 'phosphoryloxphenyl" and Substitute co -- phosphoryloxyphenyl - - Col. 9, line 26 cancel 'diethiono. . .' and substitute - - dithiono. ... -- Col. 9, line 46 cancel '(4-chlorophenyl)' and substitute -- (4-chlorophenyl)

UNITED STATES PATENT AND TRADEMARK OFFICE CERTIFICATE OF CORRECTION PATENT NO. : 4,027,037 Page 2 of 2 DATED ; May 31, 1977 INVENTOR(S) : Peter Siegle, et al. It is certified that error appears in the above-identified patent and that said Letters Patent are hereby Corrected as shown below: Col. ll, line 35 drop "CH=CH-CH- '' to join ' -NH ' so as to read -- CH=CH-CH-NH -- eigned and Sealed this thirtieth Day of August 1977

Attest.

RUTH C. MASON C. MARSHALL D ANN Attesting Officer Commissioner of Patents and Trademarks