FUNGICIDAL PREPARATIONS

Abstract: The use of certain well known very long chain quaternary n-Alkyltrimethyl ammonium salts (ATAX), alkylbenzyl-dimethyl ammonium salts (AKX) and dialkyldimethyl ammonium salts (DADAX) of general formulae (I ATAX, II AKX, and III DADAX), respectively, wherein R is straight chained or branched alkyl or alkylene with more than 17 carbon atoms, R' is straight or branched alkyl or alkylene with more than 11 carbon atoms, and X is a halogen, acetate, sulfate, or phosphate anion, of low phytotoxicity in plant protection for controlling and combating fungi, fungicidal compositions comprising such compounds either alone or in combination with other fungicidally active agents, and methods for controlling or combating fungi in plants by applying said compositions to the plants, and the use of such compounds as additives to fungicidal compositions are described.

Description: Title: Fungicidal Preparations Field of the invention; The present invention relates to the use of certain very lo chain quaternary ammonium compounds of low phytotoxicity plant protection for controlling and combating fungi. relates to fungicidal compositions comprising such compoun either alone or in combination with other fungicidally acti agents, methods for controlling or combating fungi in plants applying said compositions to the plants, and the use of su compounds as additives to fungicidal compositions. BACKGROUND OF THE INVENTION. n-Alkyltrimethyl ammonium salts (ATAX) , alkylbenzyl-dimeth ammonium salts (AKX) and dialkyldimethyl ammonium salts (DADA of the general formulae I, II, and III, respectively, are we known compounds. R* - R", X " DADAX (III For the purpose of this invention the expression very lon chain quaternary ammonium compound (VLCQAC) will be used a collective term for compounds in the ATAX (formula I) , AK (formula II) , and DADAX (formula III) series. In formulae I, II, and III above R is straight chained or branched alkyl or alkylene with more than 17 carbon atoms, R* and R" that may be the same or different are straight or branched alkyl or alkylene with more than 11 carbon atoms, and X is a halogen, acetate, sulfate, or phosphate anion. Quaternary ammonium compounds (QACs) with shorter chain lengths than VLCQACs are widely used as disinfectants and as pharma- ceutical preservatives. A vast literature on the antimicrobial activity of QACs exists and only a few representative papers are discussed here. The antimicrobial activity of some alkyltrimethyl-ammonium bromides (the ATAX-type) with n-alkyl chain lengths between C 5 and C 22 has been described by Gilbert & Al-Taae [Letters in Applied Microbiology 1, 101-104 (1985)]. It is concluded that the antimicrobial activity maximizes for n-alkyl substituent chain lengths of between 14 and 16 with bacterial strains being most sensitive towards the C 14 -compound and the fungi toward the C 16 -compound. Similarly, the effect of the n-alkyl chain length on the antimicrobial activity of AKCs with a n-alkyl chain length between C- and C 18 has been described by Daoud, Dickinson and Gilbert [Microbios 37, 73-85 (1983)]. They conclude that fungi were most sensitive towards C 12 , Gram-positive bacteria towards C , and the Gram-negative bacteria towards C 16 . In a large comparative study of the bacteriostatic, fungista- tic, and algistatic activity of fatty nitrogen compounds, Hueck, Adema, and Wiegmann [Applied Microbiology 14(3), 308- 319 (1966)] conclude that for the C 12 , C u , C 16 , and C 18 compounds in the alkyltrimethyl ammonium chloride series, the highest biostatic activity is found for the C 14 compound. In the dialkyl-dimethyl-ammoniumchloride series with n-alkyl ranging from C 8 to C 18 , the best fungistatic effect is apparently reached for the di-C 10 compound. Despite their excellent fungicidal and fungistatic properti QACs of the above types have found little use as agricultu fungicides. A recent monograph of pesticide chemistry [ tolcsy, Nadasy, and Andriska, eds. : Studies in Environmen Science 32, Pesticide Chemistry, Elsevier (1988)] only menti didecyldi ethyl ammonium bromide (DDDAB) as a compound hav a protective and curative effect against apple scab (Ventu inalqualis) . The reasons is probably to be found in the phytotoxicity the QACs. In investigations of the eradication of overwi tering apple powdery mildew (Podosphaera leucotricha (Ell. Ev.) Salm) , benzalkonium chloride, which is a mixture of C C 14 and C 16 n-alkyl benzyl dimethyl ammonium chlorides complete eradicated mildew but was very phytotoxic [Hislop & Cliffor Annals of Applied Biology 82, 557-568 (1976); Hislop, Cliffor Holgate, and Gendle: Pesticide Science 9, 12-21 (1978) Didecyl-dimethyl ammonium bromide was also phytotoxic in th study, where no other QACs were investigated. The phytotoxicity of QACs has also been noted in an invest gation of the toxicity of a number of different bactericid to Clavibacter michiσanense and to the tomato plant, Lycope sicon esculentum [Thompson: Journal of Applied Bacteriolo 61, 427-436 (1986)]. Cetyltrimethyl ammonium bromide (CTAB benzalkonium chloride and N-cetylpyrinidium chloride were ve efficient bactericides but were phytotoxic even in a conce tration of 2-20 ug/ml. As above this study was limited to t compounds mentioned. The phytotoxic effect of QACs on tomato plants has also be observed by Edgington in a study of the effect of chain leng of QACs upon their use as systemic fungicides [Edgingto Phytopathology 56, 23-25 (1966)]. He concludes that as t alkyl group of n-alkyl QACs is lengthened from ethyl to dodec in the alkyl trimethyl ammonium bromide series (using the s compounds of an even number of C-atoms in the n-alkyl chain) , the compounds become more fungitoxic, but slight necrosis of the stem is seen with the C 12 -compound. Edgington furthermore observes that the use of QACs, with more than 8 carbon atoms in the n-alkyl chain, as systemic fungicides, is limited by their adsorption to sand, roots, and xylem. The use of QACs, and especially cetyltrimethyl ammonium bro¬ mide (CTAB) , in combination with an 8-hydroxy-chinoline deri- vative and a thiabenzazol in a fungicide of low phytotoxicity when applied to seed, grain, or fruits has been described in Offenlegungsschrift DE 2342005. However, only the use of CTAB for seed, grain, and fruits is exemplified. Furthermore, the use of dicocodimethyl ammonium chloride (coco being a mixture of C 8 to C 18 -alkyl) for combating Podosphaera leucotricha on overwintering apple buds has been exemplified in Offenlegungsschrift 2408662. The Phytotoxicity of a 5% aqueous solution of didecyl dimethyl ammonium bromide (DDDAB) has been noted in this work too. No other compounds were exemplified in this study. DESCRIPTION OF THE INVENTION. From the publications summarized above it appears that the use of QACs in plant protection despite their fungicidal effects, is limited by their phytotoxicity. Furthermore, the use of VLCQACs as biocidal agents has been limited. The present invention reports for the first time the use of VLCQACs as fungicides obtaining improved disease control in plants. It has here been demonstrated that a synergistic effect of VLCQACs and another fungicidally active compound or co po- sition is often obtained. This synergistic effect allows application of the other fungicide in considerably lower dosages than the ones usually applied while still retaining the same or improved control effect of the fungal pathogen. Examples of other fungicides which can be combined with t VLCQACs of the invention include the residual fungicidal d thiocarbamates (e.g. aneb (BASF-maneb 80, BASF) and mancoz (dithane M45/LF, Kemisk Vaerk Køge, Denmark) ) , and the system fungicidal carbamates (e.g. propamocarb (Previcur ® Schering) , metal ethyl phosphonates (Fosetyl-alu iniu Rhone-Poulenc) , and acylalanines (metalaxyl, Rido il ® 5 (metalaxyl and mancozeb in combination = Ridomil ® MZ) . The diluent or carrier in the compositions of the inventio can be a solid or a liquid optionally in association with a other surface-active ingredient, for example a dispersin agent, emulsifying agent or wetting agent. Suitable surface active include nonionic agents as condensation products o fatty acid esters of polyhydric alcohol ethers, e.q. sorbita fatty acid esters, condensation products of such esters wit ethylene oxide e.q. polyoxyethylene sorbitan fatty acid esters block copolymers of ethylene oxide and propylene oxide, ace tylenic glycols such as 2,4,7,9-tetramethyl-5-decyn-4,7-diol or ethoxylated acetylenic glycols. The concentration of the VLCQACs in the compositions of th present invention when used alone or in combination with conventional fungicide, as applied to plants is preferabl within a range of 0,001 to above 1,0 per cent by weight especially 0,01 to 0,5 per cent by weight. In a primary composition or concentrate that usually should b diluted prior to application the amount of VLCQACs can var widely and can be, for example, in the range from about 1% t about 100% by weight, preferably from about 5% to 30% by weigh of the composition. The concentration of the other fungicidally active ingredien in the mixed composition of the present invention, as applie to plants is preferably within the range of 0,001 to 10 pe cent by weight , especially 0,01 to 5 per cent by weight. I a primary composition the amount of active ingredient can vary widely and can be, for example, from 5 to 80 per cent by weight of the composition. The active VLCQAC preparation or the compositions of the invention can be applied directly to the plant by, for examp¬ le, spraying or dusting either at a time when an attack of the fungus has been established and determined on the plant for combating the fungus or fungi or before the appearance of fungus as a protective measure. In both such cases the prefer¬ red mode of application is by foliar spraying. It is generally important to obtain good control of fungi in the early stages of plant growth as this is the time when the plant can be most severely damaged. The spray or dust can conveniently contain a pre- or post-emergence herbicide if this is thought necessary. Sometimes, it is practicable to treat the roots of a plant before or during planting, for example, by dipping the roots in a suitable liquid or solid composition. When the active VLCQAC preparation of the invention is applied directly to the plant a suitable rate of application is from 0.01 to 10 kg per hectare, preferably from 0.05 to 5 kg per hectare. In the following Table I the VLCQACs used in the Examples of this specification is listed. For the compound names the following abbreviations are used: L=n-C 12 H 25 (lauryl) , M=n-C 14 H 29 (myristyl) , C=n-C 16 H 33 (cetyl) , S=n-C 18 H 37 (stearyl) , Ei=n-C 20 H 41 (eicosyl) , Be=n-C 22 H 45 (behenyl) , DD=(n-C 10 H 21 ) 2 (didecyl) , DL=(n- c 12 H 25 ) 2 (dilauryl), DM=(n-C 14 H 29 ) 2 (dimyristyl) , DS=(n-C 18 H 37 ) 2 (distearyl) , T=(CH 3 ) 3 (trimethyl) , D=(CH 3 ) 2 (dimethyl), K=C 6 H 5 - CH 2 N + (benzyldimethylammonium) , and A=N + (ammonium) , and the anions B=Br " , C=C1 " . TABLE I: QACs used in the experiments, The invention is illustrated in the following examples: Example 1. LTAC, MTAC and CTAC were prepared by quaternisation of alkyldi- methylamine with methyl chloride at a pressure of 3 kg/cm 3 in water. A 25% aqueous solution was used. STAC, 20/22TAC and BeTAC were prepared by quaternisation of alk ldimethy1amine with methyl chloride at a pressure of 3 kg/cm 3 in acetone followed by crystallization. LKB was prepared by reaction of alkyldimethyl-amine in water with benzyl bromide. A 25% aqueous solution was used. EiKC was prepared by reaction of alkyl-dimethylamine with benzyl chloride in refluxing acetone followed by crystallization. The commercial product from Lonza, Bardac 22, which is a 50% solution of DDDAC in water/isopropanol mixture was used. DLDAB and DMDAB were prepared by reaction of alkyldime- thylamine with alkylbromide. DSDAC was Querton from Berol-Nobel. The identity and purity of the compounds were determined by HPLC and 13 C-NMR as well as with conventional titration techniques. The HPLC method was a modified version of the one published by Helboe [Journal of Chromatography 261. 1983, 117-122] based on chromatography of ion pairs of the QAC with an UV absorbing counterion. By using a Nucleosil CN column with methanol:water (70:30) containing 5 mM p-toluene sulphonic acid as the eluent compounds in the ATAX and the AKC series with from 12 to 22 carbons in the long alkyl chain can easily be separated. 13 C-NMR was performed on a 500 MHz spectrometer at a frequency of 125.97 MHz with simultaneous broad band decoupling. Samples were run in 10 mm tubes using CDC1 3 as solvent and as deuterium lock. The shifts obtained were in agreement with those reported by Fairchild [Journal of the American Oil Chemist Society, 59 . (7) , 1982, 305-309] except for an absorption at 25 ppm, which was not observed by Fairchild. Example 2 Phytophthora infestans on potato. Potato plants (Variety: Sava ecology, grown 14 days in 7 cm plastic pots. 1 plant/pot) were sprayed with aqueous solutions of the compounds shown in the following Table II, the concentration of active substance being listed in the Table. The solutions furthermore contained 0.1% Tween ® 20 and 5% ethanol. After spraying with the solutions the plants were incubated at 18-20°C for 24 hours after which they were inoculated with an aqueous suspension of Phytophthora infestans sporangia. Following inoculation, the potato plants were incubated in humid chambers. The dark/light interval during the incubation period was 6 hrs/18 hrs. The degree of control and phytotoxici¬ ty was assessed 6 days after the inoculation. The score of control is expressed on a scale from 0 to 9 with 9 being complete control. The phytotoxicity is evaluated on a scale from P 0 (no phytotoxicity) to P 4 (complete collapse or extinction) . The results will thus be given in the form X-P y where X is the degree of control and P is the phytotoxicity. The results are shown in the following Table II: Concentration 0.3= Compounds LTAC MTAC CTAC a -p 3 STAC 8-P 2 8- P. 7-P 0-1 20/22-TAC 8-9-P n 9-P„ 8 - p o DDDAC a -P. 2-3 9-P, 7-P- Untreated control 9-P 0 Reference 9-P 0 (6 ml Dithane/1) Inoculated control 2-P„ a) Impossible to evaluate due to the phytotoxicity. Uncertain evaluation due to the phytotoxicity. The results clearly show the remarkable effects of the VLCQACs STAC and especially 20/22-TAC, the latter being able to give control of Phytophthora infestans without causing phytotoxic effects. Example 3 Phytophthora infestans on potato plants. Potato plants were tested as in Example 2. However, Surf nol TGE (0,05%) was used as dispersing agent. The results are shown in the following Table III: TABLE III Concentration . 0 . 3^ 0 . 1? 0 . 033: Compound STAC " P 2-3 " P 2 5 " P 1 20/22 -TAC 7 " Pn 7 " Pn 5 - Pn a DLDAB - P 7 - P- 7 " p o DMDAB 5 - p o 4 ~ p c 2 " o DSDAC 7 - p o 7 " p o 5 " p o Untreated control : 9 - P„ Reference 9 - P„ Inoculated contr. : 2 - P n a) See footnote in Example 2 The present results demonstrate that inhibition of a fungal attack can be obtained without phytotoxic effects for VLCQACs both in ATAX, AKX, and the DADMX-series. The use of Surfynol ® instead of Tween ® 20, however, seems to decrease the effect of VLCQACs a little. Example 4 In vitro effect of QACs. QACs's inhibitory effect on specified stages of the life cycle of several species of Oomycetes was tested on microtiter plates. The QACs were dissolved in a dilute salts solution and the minimal inhibitory concentration (MIC) was determined. Concentrations tested were 333, 66, 13.2, 2.6, 0.5, and 0.0 xg/ml DS (= dilute salts solution [Dill and Fuller: Arch.Microbiol. 87, 92-98, 1971]). The results are shown in the following table IV: Hyphal growth 333 66 13.2 66 13.2 13.2 (3 days) Zoospore release 333 13.2 2.6 66 2.6 13.2 (2 " days) Zoospore 13.2 13.2 <0.5 <0.5 2.6 <0.5 stability Cyst-hyphae 2.6 13.2 2.6 0.5 13.2 2.6 formation (1 day) Pγthium ultimum Hyphal growth 333 66 2.6 66 13.2 2.6 (3 days) Oospore 333 66 66 333 66 13.2 germination (1 day) Oospore 66 13.2 2.6 66 13.2 0.5 formation (3 days) Phytophthora parasitica hyphal growth 66 66 2.6 66 66 2.6 (3 days) Zoosporangium 13.2 13.2 2.6 66 66 2.6 oospore formation (3 days) TABLE IV Continued 20/22 Species\ \Compound LTAC MTAC CTAC STAC -TAC DDDAC Phytophthora sp. 360-86 hyphal growth 333 13.2 2.6 66 13.2 2.6 (3 days) Oospore formation 333 2.6 2.6 66 13.2 2.6 (4 days) Phytophthora infestans sporangium 333 66 2.6 66 <0.5 2.6 germination and hyphal growth (2 days) Table IV shows that CTAC and DDDAC generally have the best score of MIC values in this test system where there are no problems with phytotoxicity. However, it is interesting to note that 20/22-TAC has the lowest MIC value for Phytophthora infestans. Example 5 Plasmopara hastedii on Sunflower. Small Sunflower plants were sprayed with aqueous solutions or suspensions of QACs approximately 24 hours before inoculation with a spore suspension of P. halstedii. The results were evaluated after 7 days, and are indicated in Table V below. TABLE V Concentration 0 . 3% 0 . 1? 0.033-= Compound LTAC " P 4 - P 4 7 ~ P 3 MTAC a " P 4 - P,. " P 3 STAC 9 " P 3 9 " P 3 9 " P 3 20/22 -TAC 9 " P 2 6 " P 0 9 " P 0 DDDAC 9 " P 2 9 " P 1 9 - P, DLDAB a " P 4 9 " P 3 DMDAB 9 " P 3 9 " p o 9 " p o DSDAC 9 - P, 5 - Pn 5 " Pn a) and ) as in Example 2. c) Stunted growth. From Table V it is apparent that VLCQACs are very efficient fungicides in this test system too. Also, it is seen that the phytotoxicity apparently poses a problem to the QACs of short chain length. Example 6 Pseudoperenospora cubensis on Cucumber. Leaves of cucumber were sprayed with aqueous solutions/ suspensions of QACs approximately 24 hours before inoculation with a spore suspension of P. cubensis. The results were evaluated after 7 days, and are shown in Table VI below. TABLE VI Concentration 0 . 35 0 . 1? 0 . 033% Compound LTAC " P 4 - P, 2 " P 1 MTAC a - P 4 2 - P 2 0 - P, CTAC a " P 4 8 " P 2 0 " P 2 STAC 7 " 1 9 - P 0 5-6 " Pn 20/22 -TAC 7 " P 0 4 " P 0 2 " Pn EiKC 5 " P 3 5 " P 1 4 - P, 0- 1 DDDAC a " P 4 " P 4 DLDAB a - P 4 0 " P 3 5 - P, DMDAB 6 - Pn 6 - P, DSDAB 8 ~ P, 5 - Pn 5 - P a) As in Example 2 The effect of VLCQACs against Pseudoperonospora cubensis on Cucumber is evident, but the optimal effect is seen with the STAC in this example. Example 7 Synergistic effect of BeTAC and Dithane ® . Potato plants were sprayed with solutions containing Dithane ® , BeTAC (dissolved in 5% aqueous ethanol) and 0.1% Tween ® 20. After 1 day, the plants were inoculated with sporangia suspen¬ sion of Phytophthora infestans and incubated 6 days at 18°C/ 18 hrs light - 13°C/6 hrs dark and a relative humidity of 80%. Evaluation of the results gave following Table VII: TABLE VII Concentration of Dithane ® ml/1 0 0 . 006 0 . 06 Concentration of BeTAC% Notation as in Example 2. An untreated control scored 9 - P n This example shows clearly the synergistic effect between the VLCQAC BeTAC and the conventional fungicide Dithane ® . Example 8 Svnerσistic effect of BeTAC and Ridomil® MZ. Potato plants were sprayed with a solution containing BeTAC and/or the fungicide Ridomil ® MZ and 0.1% W/W Tween ® 20. BeTAC was dissolved in 5% ethanol. Ridomil ® MZ was diluted to a concentration of 0.005 mg/ml (1:1000 of normal dose) . The conditions were as in Example 7. TABLE VIII Concentration of Ridomil ® MZ mg/ml 0 . 0005 0 . 005 Concentration of BeTAC in% 0 1 - p o 3 " P 0 7 " P 0 The results show that the VLCQAC BeTAC exhibits a synergistic effect in combination with Ridomil ® MZ. Example 9 QACs phytotoxicity on mono- and di-cotyledons Aqueous solutions of QACs containing 0,1% Tween 20 were sprayed on small plants until "run off". The evaluation of phytotoxi¬ city after 72 hrs is listed in Table IX. TABLE IX P 0 = Non Phytotoxic. P, •= Total extinction. As seen in the Table the VLCQAC STAC (C 18 -chain) was less phytotoxic than LKB (C 12 -chain) and MTAC (C 1 -chain) .

Claims: PATENT CLAIMS 1. A fungicidal composition comprising at least one n- Alkyl (ene) trimethyl ammonium salts , alkyl (ene) benzyl-dimethyl ammonium salts and/or dialkyl (ene) dimethyl ammonium salts (DADAX) of the general formulae I , II , and III , respectively R 1 - R" , X " DADAX (III) wherein R is straight chained or branched alkyl or alkylene with more than 17 carbon atoms, R' and R" which are the same or different, are straight or branched alkyl or alkylene with more than 11 carbon atoms , and X is a halogen, acetate, sulfate, or phosphate anion. 2 . The composition of claim 1 , wherein R is n-C 18 H 37 (stearyl) , n-C 2rj H 41 (eicosyl) , or n-C 22 H 45 (behenyl) , R* =R"are n- C 12 H 25 (lauryl) , n-C 14 H 29 (myristyl) , n=C 16 H 33 (cetyl) , n-C 18 H 37 (stearyl) , n-C 20 H 41 (eicosyl) or n-C 22 H 45 (behenyl) , and X is B=Br " , C=C1 " , Ac=acetate, S=sulfate, or P=phosphate. 3. The composition of claim 1 or 2, wherein R is stearyl and/or behenyl. 4. The composition of any of claims 1 to 3, comprising a mixture of compounds wherein R is eicosyl and behenyl. 5. The composition of any of claims 1 to 4, comprising a further fungicidally active agent. 6. The composition of claim 5, wherein said further fungicidally active agent is chosen from the group comprising residual fungicidal dithiocarbamates, systemic fungicidal carbamates, metal ethyl phosphonates, and acylalanines, or mixtures thereof. 7. The composition of claim 6, wherein said dithiocarba- mate(s) are chosen from aneb and mancozeb. 8. The composition of claim 6, wherein said carbamate(s) is propamocarb. 9. The composition of claim 6, wherein said acylalanine(s) is metalaxyl. 10. The composition of any of the claims 1 to 9, wherein said salt(s) is present in an amount of from 0.001% by weight to above 1.0% by weight, preferably from 0.01% by weight to 0.5% by weight. 11. A concentrate or primary composition of any of claims 1 to 9, wherein said salt(s) is present in an amount of from 1% to 100% by weight, preferably from 5% to 30% by weight. 12. The composition of any of claims 5 to 10, wherein said further fungicidally active agent is present in an amount of from 0.001% to 30% by weight. 13. The concentrate of claim 11, wherein a further fungicidally active agent is present in an amount of from 5% to 80% by weight. 14. A method of controlling plant pathogenic fungi including yeast in plants, wherein a fungicidally active amount of a composition as claimed in any of claims 1 to 13 is applied to said plants. 15. The method of claim 14, wherein the fungi to be controlled belong to the Mastioomvcotina. 16. The method of claim 15, wherein the fungi to be controlled belong to the Oomvcetes. 17. The method of claim 16, wherein the fungus to be controlled is a Phytophthora or Pythium. 18. The method of any of claims 14 to 17, wherein the plants whereto said composition is applied belong to the dicotyledons. 19. The method of claim 18, wherein said plant is chosen from the group comprising sun flower, tomato, cucumber, and potato. 20. The method of claim 19, wherein said plant is potato. 21. The method of any of claims 14 to 20, wherein said composition is applied to said plants prior to, at the outset, or after establishment and detection of an attack by fungi by spraying or dusting, preferably by foliar spraying. 22. The method of any of claims 14 to 20, wherein said composition is applied to the roots of said plants prior to or during planting by dipping said roots into a liquid composition of any of the claims 1 to 13. 23. The method of any of the claims 14 to 22, wherein said composition is applied in an amount of from 0.01 kg/ha to 10 kg/ha, preferably in an amount of from 0.05 kg/ha to 5 kg/ha. 24. Use of at least one compound as defined by one of the formulae I, II, and III in any of claims 1 to 4 as an additive to a fungicidally active composition or compound. 25. Use of stearyl trimethyl ammonium chloride as an additive to a fungicidally active composition or compound. 26. Use of behenyl trimethyl ammonium chloride as additive to a fungicidally active composition. 27. Use of a mixture of eicosyl and behenyl trimethyl ammonium chloride as an additive to a fungicidally active composition or compound.

Inventors: DAMTOFT SOEREN, LANGE LENE, SVENDSEN NANNETTE, DAMTOFT, SOEREN, LANGE, LENE, SVENDSEN, NANNETTE
Applicants: FERROSAN FINE CHEM AS, NOVONORDISK AS, FERROSAN FINE CHEMICALS A/S, NOVO NORDISK A/S
Application year: 1991
Main classification: A01N37
IPC codes: A01N33