Патент USA US2127879код для вставки
I Patented 2,127,879 23, ‘1938 ‘Y 1 UNITED‘ STATES PATENT OFFICER 1 2.12am on. m m ms'rrnoor'md ; msnwuann Us]: > - um Martin, Basel, Switserland, alalgnor' to the?nn o! I. IL'Geigy 8. A" Basel,‘ Swltlcr No' Drawing. ‘Application mm." 2a, 1031. so its?‘ No. 123.061. In Germany, February 7L i 11 cums, (01. 161-31) Instead of CH; other alkyl or aralkyl and aryl tain the live or six'sided atomic ring group groups such as ethyl, butyl, amyl, benzyl, phenyl, It has been found that compounds which con- ' ' ethyl,- phenyl, p-chlorophenyl may be present. 00 (4) Benzotet'ronlc-acid-s-carboxylic acid-ben , “ \o?-co-n zylester \ 2*‘) , 0 00 in the molecule are valuable insect combatting agents. . \ In the above formula: . - group. (5) Benzotetronic acid-m-carboxylic acid-amide and can at the same time be a. member of ' co R represents —0-alkyl. --O-aralkyl, '--NH:, —NH-alkyl, —NH-aryl, NH-- and N=cyclo guanyl radicals, other nitrogen-containing I a (6) Benzotetronic acid-a-carboxylic acid-pi ’ peridide ‘Such compounds are for example: '(1) Tetronic-a-csrboxylic acid ester - ' - , co ' / Y cur-om ' ' )cn-co-né 0/ O CH1 on, > CHr-CBI/ The nitrogen atom may bear other divalent cyclo alkyl radicals, nicotine or anabasine being em '30 ployed in the place of piperidine. 0 , wherein alkyl vis represented by the groups CH1.‘ vCiHs, C3111; C4110, 651111. In the place of [(7) Benzotetronic ‘acid-u-carbonylic ‘acid-‘ure ide at. 3.5' .\ . I co acn-cofnn-‘co-Nm ' in the ‘above formula there can be they grouping ’ 0/ cam-0n (8) Benzotetronic guanidide l (2) Dehydracetic V l acid _ acid - a - carboxylic ' ' _ \ 40 . aCH-CO-NH-f-(f-NE o CH:— acid , co CH/C0\aCH-CO-CH:, 45 o or the custom‘, CaH-z, CsHo, CsHu amide thereof radicals or ring‘ systems, or simple or substi; '40 'H 0/ stituted tertiaryv amino groups, ureido- and tuted alkyl-, ar'alkyl- or aryl groups. \ _ \uCH—CO-—N<H alkyl or corresponding single or mixed sub- _ 20 10 from OH: to CsHu may also replace the benzyi rated or unsaturated,‘ unsubstituted or sub stituted carbon bridge which closes the ring further ring systems, and , 'I‘he'chlorobenzyl, phenylethyl or alkyl radicals x represents a single‘ or double membered, satu ‘ \ wn-co-o-cm-O o/to . I H s 0/ (9)‘ Benzotetronic acid-a-carboxylicacld-anilide O o The two methyl groups can 8also be replaced by .one or two phenyl groups. - ' (3) a-Aceto-benzotetronic acid ‘ CO . -, :OILCO-CH: 0/o Instead of the phemrlradlcal there may be men tioned tolyl, unsubstituted or substituted amino phenyl, mono- or dichloro-phenyl, ¢_-/p-naphtbyl, . , , 2 2,127,a're cyclohexyl, methyl-cyclohexyl, diethylaminoeth ylene and similar radicals. (10) Benzotetronic methylanllide acid-a-carboxylic CO acid skin (according to Anschiitz, Annalen der Chemie. 1909, 887, page 201, halogen cumarines produce blisters on the skin and strong itching) ; in addi tion they are quite colourless, which is an ad vantage over the yellow coloured thiocumarine; the latter feature is particularly important as regards the use of these insect combatting agents CH: aCH-C O—N 0/0 on textiles. 10 I The above mentioned insect combatting agents The alkyl group may vary from CH: to CsHn; instead of the phenyl radical there may be at the same place the groups mentioned below of 15 Formula 9. (11) Benzotetronic acid-a-carboxylic acid phenyl-hydrazide. 10 can be employed by. the usual processes. Solu tions in water or in cheap organic solvents can be used for spreading, sprinkling or dipping the materials and textiles to be protected; they can also be atomized without harmful effects being 15 noticed on warm-blooded beings. Pelts, feathers The phenylradical may also be substituted by or wool treated with such solutions can be pro tected in a lasting manner against moths. Pre cipitation of the effective substance from alkaline solution on to the article to be protected by 20 means of acid leads to the same result. If plant parasites are sprayed it will be found, for example one or more halogen atoms. on ?ies or walking-sticks that the poisoning ef 20 0/. ° v25 -. .\ fective and in\\par't more bearable to the human (12) ‘2.3 - naphthotetronic acid - a - carboxylic acid-ester v ' - The following examples illustrate the invention, the parts being by weight: o/0 30 feet by contact is very good. Furthermore, solutions or emulsions in oils, 25 creams, fats may be used or the compounds may be added to powders or they may be used in any form usual for combatting insects. ' The alkyl group may vary from CH: to CsHn.' - 30 Example I The atom grouping 2 parts of dehydracetic acid are dissolved in 98 parts. of alcohol; pelts, feathers or wool are 3'5 treated for example by dipping, then centrifuged and dried. The goods so treated are moth proof. 86 Quite dilute solutions sumce to obtain a satis 0 is an essential part of all these compounds, X 40 being a single or two membered carbon bridge. Through the substitution by three CO groups, factory protection against moths. If instead of the above mentioned dehydracetic acid, use be made of derivatives of tetronic acids, as dichlorbenzo- or benzotetronic acid the hydrogen atom of the a-carbon atom becomes such carboxylic acid ester, for example the methyl-, very reactive, wherefore compounds of this kind ‘ethyl-, propyl-, amyl- and other esters, or other have a strongly acid character. They therefore dissolve easily in alkalies and can be precipitated mentioned a-ketosubstituted tetronic acid deriva tives such as ketones, carboxylic acid-amides, again by the addition of strong acids. By suitable -anilides or -diethylethylenediamides, an equiva substitution in the groups linked to the above lent effect is obtained. typical atom grouping the solubility in water or or ganic solvents can be altered and the physiologi 50 cal effectiveness in?uenced. In particular amino or halogen substituents in the aromatic and ali phatic side groups have notable in?uence. Substituted condensation products of un saturated aromatic hydroxy-acids have already . been proposed as insect destroying agents. Under these fall halogen substitution products of cumarine or the homologues thereof or the de rivatives thereof, all substances containing a substituted pyrone ring. Fluo-, bromo-, chloro-, 00 alkyl, aryl- and thio-cumarines are named. The type of compound used in the present process can be termed an a-keto-y-lakton, in which how ever to obtain remarkable effectiveness an addi tional -CO-group must be bound to the a-posi tion carbon atom. Chemical consideration of the structure of these curamine derivatives in com parison with the present a-ketotetronic acids 40 Certain parasites such as walking-sticks are killed by spraying with the above mentioned alco holic solutions. The said compounds are. also’ good when used as contact agents against ?ies. Example II A concentrated aqueous solution of the com pounds mentioned in Example I, is made with the aid of alkalies, the material to be treated dipped therein and then acidi?ed, whereby a sat isfactory protection against insects is again ob ’ tained. What I claim is: 1. A devitalizing composition of matter for 60 combatting pests of the insect class, containing as its essential active ingredient a compound represented by the formula / 65 (a-carbonyltetronic acids) immediately shows the fundamental difference between them. De hydracetic acid which is outstandingly effective, behaves chemically entirely differently from a‘ cumarine. The same applies to the a-kEtOSllb stituted tetronic acids. ' ' Compared with the cumarine derivatives men 75 tioned above, they are in part notably more ef X being a ring closing grouping selected from the groups 70 -cm-, >CH-lower alkyl, -—CH=(|J—- , —CH=C—-, CH| cHl phe'nylene, 'naphthylene, and R. being a mem 75 3 2,127,879 ber of the group consisting of —0.lower alkyl, . as its essential active ingredient a compound --O.arallryl, —-N'Hz, —NH.lower alkyl, -NI-I.aryl, represented by the formula aryllllower alkyl, -NH— and —N=cycloalwl. 00 acH-c0-c.ni.+1 lower alkyl, aralkyl and phenyl. 2. A devitalizing composition of matter for 0 . combatting. pests of the insect class, containing 0/ as its essential active ingredient a compound represented by the formula 10 00 n being a number from 1 to 5. a 6. A devitalizing composition of matter for combatting pests of the insect class, containing 10 ° \wnJL-R as its essential active ingredient a compound represented by the formula 0 00 0/ - “on-coo c.H,.+1 15 B being a member of the group consisting of alkyl, —-NH.aryl, aryllTlZlower alkyl, —N'H—- and -—N=cycloalky1, lower alkyl, aralkyl and phenyl. 20 3. A devitalizing composition of matter for combatting pests of the insect class, containing as its essential active ingredient a compound 15 o —O.lower alkyl, —0.aralkyl, —NH:, -NH.lower 0/ n being a number from 1 to 5. _ - 7. A devitalizing composition of matter for combatting pests of the insect class, containing‘as 20 its essential active‘ ingredient a compound repre sented by the formula represented by the formula 00 25 0 Emma-on GR 0, 0/ ' B being a member of the group consisting of zero R being a member of the group consisting of and CH3. , 30 lower alkyl and aralkyl. 4. A devitalizing composition of matter for 8. A devitalizins composition of matter for 30 combatting pests of the insect class, containing combatting pests of the insect class, containing as its essential active ingredient ¢-aceto—benao as its essential active ingredient a compound tetronic acid. represented ‘by the formula , 9. A devitalizing composition of matter for _ combatting pests of the insect class, containing as its essential active ingredient u-carbanilido benzctetronic acid. 0 . X: 0/ wherein X1 is a member of the group consisting of H, lower alkyl, aryl of the benzene and naph thalene series, monovalent cycloalkyl radicals, and X: is a member of the group consisting of H, lower alkyl, aryl of the benzene series, X1 and x: being together a divalent cycloalkyl radical. 5. A devitalizlng composition of matter for combatting pests of the insect class. containing 25 10. A devitalizing composition of matter for combatting pests of the insect class, containing. as its essential active ingredient benzotetronic acid ethyl ester. 11. A method of protecting materials against pests of the insect class, comprising treating the materials first‘ with a strong alkaline aqueous solution of a compound named in claim 1 and thereupon with an acid agent. HENRY MARTIN.