Patent Publication Number: US-2009221588-A1

Title: Fungicidal compositions

Description:
The present invention relates to novel fungicidal compositions suitable for control of diseases caused by phytopathogens, especially phytopathogenic fungi and to a method of controlling diseases on useful plants. 
     It is known from WO 04/35589 and WO 04/58723 that certain carboxamides have biological activity against phytopathogenic fungi. On the other hand various fungicidal compounds of different chemical classes are widely known as plant fungicides for application in various crops of cultivated plants. However, crop tolerance and activity against phytopathogenic plant fungi do not always satisfy the needs of agricultural practice in many incidents and aspects. 
     Out of the above-mentioned needs of agricultural practice for increased crop tolerance and/or increased activity against phytopathogenic fungi, there is therefore proposed in accordance with the present invention a novel composition suitable for control of diseases caused by phytopathogens comprising 
     (A) a compound of formula I 
     
       
         
         
             
             
         
       
     
     or a compound of formula II 
     
       
         
         
             
             
         
       
     
     wherein R 1b  is difluoromethyl or trifluoromethyl and R 2b  is alkyl, alkoxyalkyl or haloalkyl, or tautomers of such compounds; and
 
(B) a compound selected from the group consisting of
 
a compound of formula B-1
 
     
       
         
         
             
             
         
       
     
     wherein
 
p is an integer equal to 1, 2, 3 or 4,
 
q is an integer equal to 1, 2, 3, 4 or 5,
 
r is an integer equal to 0 or 1,
 
each substituent X is chosen, independently of the others, as being halogen, alkyl, haloalkoxy or haloalkyl,
 
each substituent Y is chosen, independently of the others, as being halogen, alkyl, alkenyl, alkynyl, haloalkyl, alkoxy, amino, phenoxy, alkylthio, dialkylamino, acyl, cyano, ester, hydroxy, aminoalkyl, benzyl, haloalkoxy, halosulphonyl, halothioalkyl, alkoxyalkenyl, alkylsulphonamide, nitro, alkylsulphonyl, phenylsulphonyl or benzylsulphonyl,
 
a compound of formula B-2
 
     
       
         
         
             
             
         
       
     
     a compound of formula B-3 
     
       
         
         
             
             
         
       
     
     a compound of formula B-4 
     
       
         
         
             
             
         
       
     
     a compound of formula B-5 
     
       
         
         
             
             
         
       
     
     wherein
 
R 1  is hydrogen or fluoro,
 
R 2  is halogen, alkyl, haloalkyl, alkoxy, haloalkoxy or —C(R 4 )═N—OR 5 ,
 
R 3  is hydrogen, halogen, alkyl or haloalkyl,
 
R 4  is hydrogen or methyl,
 
R 5  is alkyl, alkenyl or alkynyl,
 
     A is 
     
       
         
         
             
             
         
       
     
     R 6  is alkyl,
 
R 7  is halogen, alkyl or haloalkyl,
 
R 8  is hydrogen or halogen,
 
R 9  is halogen or alkyl,
 
R 10  is halogen, alkyl or haloalkyl,
 
a compound of formula B-6
 
     
       
         
         
             
             
         
       
     
     wherein
 
R 11  is hydrogen, halogen, alkyl or haloalkyl,
 
     Q is 
     
       
         
         
             
             
         
       
     
     R 12  is alkyl,
 
R 13  is hydrogen or halogen,
 
R 14  is halogen, alkyl or haloalkyl,
 
R 15  is halogen, alkyl or haloalkyl;
 
a compound of formula B-7
 
     
       
         
         
             
             
         
       
     
     and a compound of formula B-8 
     
       
         
         
             
             
         
       
     
     It has been found that the use of component (B) in combination with component (A) surprisingly and substantially enhance the effectiveness of the latter against fungi, and vice versa. Additionally, the method of the invention is effective against a wider spectrum of such fungi that can be combated with the active ingredients of this method, when used solely. 
     A further aspect of the present invention is a method of controlling diseases on useful plants or on propagation material thereof caused by phytopathogens, which comprises applying to the useful plants, the locus thereof or propagation material thereof a composition according to the invention. Preferred is a method, which comprises applying to the useful plants or to the locus thereof a composition according to the invention. Further preferred is a method, which comprises applying to the propagation material of the useful plants a composition according to the invention. 
     For the purposes of the present invention, halogen appearing in the substituent definitions means typically chlorine, bromine, iodine of fluorine. 
     For the purposes of the present invention, each of the alkyl or acyl radicals appearing in the substituent definitions typically contains from 1 to 10 carbon atoms, preferentially from 1 to 7 carbon atoms, more preferentially from 1 to 5 carbon atoms, and may be linear or branched. The alkyl radicals appearing in the substituent definitions are, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, hexyl and the branched isomers of pentyl and hexyl. 
     For the purposes of the present invention, each of the alkenyl or alkynyl radicals appearing in the substituent definitions typically contains from 2 to 10 carbon atoms, preferentially from 2 to 7 carbon atoms, more preferentially from 2 to 5 carbon atoms, and may be linear or branched. 
     The compound of formula I, 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid (9-isopropyl-1,2,3,4-tetrahydro-1,4-methano-naphthalen-5-yl)-amide, occurs in four different stereoisomers, which are described as the single enantiomers of formulae I I , I II , I III , and I IV : 
     
       
         
         
             
             
         
       
     
     The invention covers all such stereoisomers and mixtures thereof in any ratio. 
     According to the invention “racemic syn-3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid (9-isopropyl-1,2,3,4-tetrahydro-1,4-methano-naphthalen-5-yl)-amide” or “racemic syn-compound of formula (I)” means a racemic mixture of compounds of formula I I  and I II . 
     According to the invention “racemic anti-3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid (9-isopropyl-1,2,3,4-tetrahydro-1,4-methano-naphthalen-5-yl)-amide” or “racemic anti-compound of formula (I)” means a racemic mixture of compounds of formula I III  and I IV . 
     A preferred embodiment of the invention is represented by those compositions which comprise as component A) the compound of formula (I). 
     One embodiment is represented by those compositions which comprise as component A) the racemic syn-compound of formula (I). Another embodiment is represented by those compositions which comprise as component A) the racemic anti-compound of formula (I). Yet another embodiment is represented by those compositions which comprise as component A) mixture of the racemic syn- and anti-compound of formula (I), in a syn/anti-ratio of from 1:1 to 100:1, for example 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, 20:1, 50:1 or 100:1. Preference is given to ratios from 2:1 to 100:1, more preferably 4:1 to 10:1. 
     The compound of formula I and its manufacturing processes is described in WO 04/35589. The compound of formula I can be prepared by reacting an acid chloride of formula III 
     
       
         
         
             
             
         
       
     
     with an amine of formula IV 
     
       
         
         
             
             
         
       
     
     The acid chloride of formula III can be produced by using difluoroacetic acid ethyl ester as starting material, which can be reacted to 4,4-difluoro-3-oxo-butyric acid ethyl ester as described in example H1: 
    
    
     EXAMPLE H1 
     4,4-Difluoro-3-oxo-butyric acid ethyl ester 
     A solution of 12.4 g difluoroacetic acid ethyl ester (0.1 mol) and 88.1 g of acetic acid ethyl ester (10 equivalents) was heated at 70° C. Sodium ethylate solution (20% in ethanol, 1.1 equivalents) was added within 1 hour and the mixture was stirred for 4 hours at 70° C. The reaction mixture was acidified with a ethyl acetate/HCl-solution and precipitates were removed by filteration. The solvent was removed by distillation and 17.2 g of 4,4-difluoro-3-oxo-butyric acid ethyl ester were obtained (purity: 78.2%; yield: 81.0%). 
     The obtained 4,4-difluoro-3-oxo-butyric acid ethyl ester can be transformed into the acid chloride of formula III according to the method as described in U.S. Pat. No. 5,093,347. 
     The amine of formula IV can be produced according to scheme 1. 
     
       
         
         
             
             
         
       
     
     The 9-isopropylidene-5-nitro-benzonorbornadiene of formula D′ can be synthesized through Diels-Alder addition of an in situ generated benzyne B′ [for example starting from a 6-nitroanthranilic acid of formula (A′) by diazotation with t-butyl nitrite as described in example H2]. 
     The 6,6-dimethylfulvene of formula C′ is available according to M. Neuenschwander et al,  Helv. Chim. Acta,  54, 1037 (1971), ibid 48, 955 (1965). R. D. Little et al,  J. Org. Chem.  49, 1849 (1984), I. Erden et al,  J. Org. Chem.  60, 813 (1995) and S. Collins et al,  J. Org. Chem.  55, 3395 (1990). 
     The aniline of formula IV may be obtained by a one-pot reaction from the compound of formula D′ via exhaustive hydrogenation as described in examples H3 and H4. 
     EXAMPLE H2 
     9-Isopropylidene-5-nitro-benzonorbornadiene 
     A mixture of 6-nitroanthranilic acid (110.4 g, 0.6 mol) and 6,6-dimethylfulvene (98.5 g, 1.5 eq.) in 700 ml dimethoxyethane was added dropwise to a solution of t-butyl nitrite (96.3 g, 1.4 eq.) in 2 litre 1,2-dimethoxyethane under N 2 -atmosphere at 72° C. within 20 minutes. A vigorous formation of gas started immediately and the temperature rose to 79° C. Gas formation ceased after 30 min. After 3 h at reflux temperature the mixture was cooled to room temperature, evaporated and purified on silica gel in hexane-ethyl acetate 95:5 resulting in 76.7 g of 9-isopropylidene-5-nitro-benzonorbornadiene as a yellow solid (m.p. 94-95° C.). 
     EXAMPLE H3 
     9-Isopropyl-5-amino-benzonorbornene: syn-enrichment 
     35.9 g 9-isopropylidene-5-nitro-benzonorbornadiene in 400 ml tetrahydrofurane were exhaustively hydrogenated in the presence of 25 g 5% Rh/C over 106 h. Filtration and evaporation of the solvent resulted in 32.15 g 9-isopropyl-5-amino-benzonorbornene in the form of an oil (syn/anti-ratio 9:1; yield: 97.4% of theory). 
     EXAMPLE H4 
     9-Isopropyl-5-amino-benzonorbornene: anti-enrichment 
     41.41 g 9-isopropylidene-5-nitro-benzonorbornadiene in 1 litre tetrahydrofurane were exhaustively hydrogenated for four hours in the presence of 22 g 5% Pd/C at room temperature and atmospheric pressure. Filtration and evaporation followed by purification on silica gel in hexane-ethyl acetate-7:1 gave 29.91 g 9-isopropyl-5-amino-benzonorbornene (syn/anti-ratio 3:7; yield: 81.5%) in the form of an oil. 
     The compounds of formula B-1 and their manufacturing processes are described in WO 04/16088 and WO 05/77179. A preferred compound of formula B-1 is the compound of formula B-1.1 
     
       
         
         
             
             
         
       
     
     which is described in WO 04/16088, registered under CAS-Reg. No.: 658066-35-4 and is also known as fluopyram. 
     The compound of formula B-2 is described in WO 00/65913 and registered under CAS-Reg. No.: 304911-98-6; the compound of formula B-3 is described in EP-1-243-584-A1 and registered under CAS-Reg. No.: 304900-25-2; the compound of formula B-4 is described in WO 99/24413 and registered under CAS-Reg. No.: 224049-04-1; the compound of formula B-7 is registered under CAS-Reg. No.: 871513-08-5; and the compound of formula B-8 is registered under CAS-Reg. No.: 688046-51-7. 
     The compounds of formula B-5 and their manufacturing processes are described in WO 03/70705, WO 02/8197, WO 03/66609 and WO 03/66610. A preferred compound of formula B-5 is N-(3′,4′-dichloro-5-fluoro-1,1′-biphenyl-2-yl)-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide, herein also referred to as “compound B-5.1”, which is described in WO 03/70705, registered under CAS-Reg. No.: 581809-46-3 and is also known as bixafen. 
     The compounds of formula B-6 and their manufacturing processes are described in WO 03/10149, JP-A-10-251240, DE-A-103-03-589, EP-0-824-099-A1 and DE-A-102-29-595. A preferred compound of formula B-6 is N-[2-(1,3-dimethylbutyl)-phenyl]-5-fluoro-1,3-dimethyl-1H-pyrazole-4-carboxamide, herein also referred to as “compound B-6.2”, which is described in WO 03/10149. 
     Examples of especially suitable compounds as component (B) are compounds selected from the following group P, which consists of 35 compounds: 
     Group P: especially suitable compounds as component (B) in the compositions according to the invention: 
     the compound of formula B-1.1 
     
       
         
         
             
             
         
       
     
     the compound of formula B-1.2 
     
       
         
         
             
             
         
       
     
     the compound of formula B-1.3 
     
       
         
         
             
             
         
       
     
     the compound of formula B-1.4 
     
       
         
         
             
             
         
       
     
     the compound of formula B-2;
 
the compound of formula B-3;
 
the compound of formula B-4;
 
N-(3′,4′-dichloro-5-fluoro-1,1′-biphenyl-2-yl)-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide (compound B-5.1); 3-(difluoromethyl)-N-{3′-fluoro-4′-[(E)-(methoxyimino)-methyl]-1,1′-biphenyl-2-yl}-1-methyl-1H-pyrazole-4-carboxamide (compound B-5.2); 3-(trifluoromethyl)-N-{3′-fluoro-4′-[(E)-(methoxyimino)-methyl]-1,1′-biphenyl-2-yl}-1-methyl-1H-pyrazole-4-carboxamide (compound B-5.3); N-(3′,4′-dichloro-1,1′-biphenyl-2-yl)-5-fluoro-1,3-dimethyl-1H-pyrazole-4-carboxamide (compound B-5.4); N-(4′-chloro-3′-fluoro-1,1′-biphenyl-2-yl)-2-methyl-4-(trifluoromethyl)-1,3-thiazole-5-carboxamide (compound B-5.5); N-(4′-chloro-1,1′-biphenyl-2-yl)-4-(difluoromethyl)-2-methyl-1,3-thiazole-5-carboxamide (compound B-5.6); N-(4′-bromo-1,1′-biphenyl-2-yl)-4-(difluoromethyl)-2-methyl-1,3-thiazole-5-carboxamide (compound B-5.7); 4-(difluoromethyl)-2-methyl-N-[4′-(trifluoromethyl)-1,1′-biphenyl-2-yl]-1,3-thiazole-5-carboxamide (compound B-5.8); N-(4′-chloro-3′-fluoro-1,1′-biphenyl-2-yl)-4-(difluoromethyl)-2-methyl-1,3-thiazole-5-carboxamide (compound B-5.9); N-[2-(1,3-dimethylbutyl)-phenyl]-1,3-dimethyl-1H-pyrazole-4-carboxamide (compound B-6.1); N-[2-(1,3-dimethylbutyl)-phenyl]-5-fluoro-1,3-dimethyl-1H-pyrazole-4-carboxamide (compound B-6.2); N-[2-(1,3-dimethylbutyl)-phenyl]-5-chloro-1,3-dimethyl-1H-pyrazole-4-carboxamide (compound B-6.3); 3-(difluoromethyl)-N-[2-(1,3-dimethylbutyl)-phenyl]-1-methyl-1H-pyrazole-4-carboxamide (compound B-6.4); 3-(trifluoromethyl)-N-[2-(1,3-dimethylbutyl)-phenyl]-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide (compound B-6.5); 3-(trifluoromethyl)-N-[2-(1,3-dimethylbutyl)-phenyl]-5-chloro-1-methyl-1H-pyrazole-4-carboxamide (compound B-6.6); 1,3-dimethyl-N-[2-(1,3,3-trimethylbutyl)-phenyl]-1H-pyrazole-4-carboxamide (compound B-6.7); 5-fluoro-1,3-dimethyl-N-[2-(1,3,3-trimethylbutyl)-phenyl]-1H-pyrazole-4-carboxamide (compound B-6.8); 3-(difluoromethyl)-1-methyl-N [2-(1,3,3-trimethylbutyl)-phenyl]-1H-pyrazole-4-carboxamide (compound B-6.9); 3-(trifluoromethyl)-1-methyl-N-[2-(1,3,3-trimethylbutyl)-phenyl]-1H-pyrazole-4-carboxamide (compound B-6.10); 3-(trifluoromethyl)-5-fluor-1-methyl-N-[2-(1,3,3-trimethylbutyl)-phenyl]-1H-pyrazole-4-carboxamide (compound B-6.11); 3-(trifluoromethyl)-5-chloro-1-methyl-N-[2-(1,3,3-trimethylbutyl)-phenyl]-1H-pyrazole-4-carboxamide (compound B-6.12); N-[2-(1,3-dimethylbutyl)-phenyl]-2-iodobenzamide (compound B-6.13); 2-iodo-N-[2-(1,3,3-trimethylbutyl)-phenyl]-benzamide (compound B-6.14); N-[2-(1,3-dimethylbutyl)-phenyl]-2-(trifluoromethyl)-benzamide (compound B-6.15); 2-(trifluoromethyl)-N-[2-(1,3,3-trimethylbutyl)-phenyl]-benzamide (compound B-6.16); 3-(trifluoromethyl)-N-[2-(1,3-dimethylbutyl)-phenyl]-1-methyl-1H-pyrazole-4-carboxamide (compound B-6.17);
 
the compound of formula B-7;
 
and the compound of formula B-8.
 
     Throughout this document the expression “composition” stands for the various mixtures or combinations of components (A) and (B), for example in a single “ready-mix” form, in a combined spray mixture composed from separate formulations of the single active ingredient components, such as a “tank-mix”, and in a combined use of the single active ingredients when applied in a sequential manner, i.e. one after the other with a reasonably short period, such as a few hours or days. The order of applying the components (A) and (B) is not essential for working the present invention. 
     The compositions according to the invention may also comprise more than one of the active components (B), if, for example, a broadening of the spectrum of phytopathogenic disease control is desired. For instance, it may be advantageous in the agricultural practice to combine two or three components (B) with component (A). An example is a composition comprising a compound of formula (I), a compound of formula B-1.1 and a compound of formula B-2. 
     One embodiment of the invention is represented by those compositions, wherein (A) is a compound of formula (I) and (B) is a compound selected from the group consisting of a compound of formula B-1, a compound of formula B-2, a compound of formula B-3, a compound of formula B-4, a compound of formula B-5 and a compound of formula B-6. 
     The following compositions are preferred: 
     A composition comprising (A) a compound of formula (I) and (B) a compound selected from the group P. 
     A composition comprising (A) a compound of formula (I) and (B) a compound of formula B-1.1. 
     A composition comprising (A) a compound of formula (I) and (B) a compound of formula B-2. 
     A composition comprising (A) a compound of formula (I) and (B) a compound of formula B-3. 
     A composition comprising (A) a compound of formula (I) and (B) a compound of formula B-4. 
     A composition comprising (A) a compound of formula (I) and (B) a compound of formula B-5. 
     A composition comprising (A) a compound of formula (I) and (B) a compound of formula B-5, wherein A is A1. 
     A composition comprising (A) a compound of formula (I) and (B) the compound B-5.1. 
     A composition comprising (A) a compound of formula (I) and (B) a compound of formula B-6. 
     A composition comprising (A) a compound of formula (I) and (B) a compound of formula B-6, wherein Q is Q1. 
     A composition comprising (A) a compound of formula (I) and (B) the compound B-6.2. 
     A composition comprising (A) a compound of formula (I) and (B) a compound of formula B-7. 
     A composition comprising (A) a compound of formula (I) and (B) a compound of formula B-8. 
     A further preferred embodiment of the invention is represented by those compositions, wherein (A) is a compound of formula II and (B) is a compound selected from the group P. 
     A further preferred embodiment of the invention is represented by those compositions, wherein (A) is a compound of formula IIa 
     
       
         
         
             
             
         
       
     
     and (B) is a compound selected from the group P. 
     A further preferred embodiment of the invention is represented by those compositions, wherein (A) is a compound of formula lib 
     
       
         
         
             
             
         
       
     
     and (B) is a compound selected from the group P. 
     A further preferred embodiment of the invention is represented by those compositions, wherein (A) is a compound of formula IIc 
     
       
         
         
             
             
         
       
     
     and (B) is a compound selected from the group P. 
     A further preferred embodiment of the invention is represented by those compositions, wherein (A) is a compound of formula IId 
     
       
         
         
             
             
         
       
     
     and (B) is a compound selected from the group P. 
     A further preferred embodiment of the invention is represented by those compositions, wherein (A) is a compound of formula IIe 
     
       
         
         
             
             
         
       
     
     and (B) is a compound selected from the group P. 
     The compositions according to the invention are effective against harmful microorganisms, such as microorganisms, that cause phytopathogenic diseases, in particular against phytopathogenic fungi and bacteria. 
     The compositions according to the invention are effective especially against phytopathogenic fungi belonging to the following classes: Ascomycetes (e.g.  Venturia, Podosphaera, Erysiphe, Monilinia, Mycosphaerella, Uncinula ); Basidiomycetes (e.g. the genus  Hemileia, Rhizoctonia, Phakopsora, Puccinia, Ustilago, Tilletia ); Fungi imperfecti (also known as Deuteromycetes; e.g.  Botrytis, Helminthosporium, Rhynchosporium, Fusarium, Septoria, Cercospora, Alternaria, Pyricularia  and  Pseudocercosporella ); Oomycetes (e.g.  Phytophthora, Peronospora, Pseudoperonospora, Albugo, Bremia, Pythium, Pseudosclerospora, Plasmopara ). 
     According to the invention “useful plants” typically comprise the following species of plants: grape vines; cereals, such as wheat, barley, rye or oats; beet, such as sugar beet or fodder beet; fruits, such as pomes, stone fruits or soft fruits, for example apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries or blackberries; leguminous plants, such as beans, lentils, peas or soybeans; oil plants, such as rape, mustard, poppy, olives, sunflowers, coconut, castor oil plants, cocoa beans or groundnuts; cucumber plants, such as marrows, cucumbers or melons; fibre plants, such as cotton, flax, hemp or jute; citrus fruit, such as oranges, lemons, grapefruit or mandarins; vegetables, such as spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, cucurbits or paprika; lauraceae, such as avocados, cinnamon or camphor; maize; tobacco; nuts; coffee; sugar cane; tea; vines; hops; durian; bananas; natural rubber plants; turf or ornamentals, such as flowers, shrubs, broad-leaved trees or evergreens, for example conifers. This list does not represent any limitation. 
     The term “useful plants” is to be understood as including also useful plants that have been rendered tolerant to herbicides like bromoxynil or classes of herbicides (such as, for example, HPPD inhibitors, ALS inhibitors, for example primisulfuron, prosulfuron and trifloxysulfuron, EPSPS (5-enol-pyrovyl-shikimate-3-phosphate-synthase) inhibitors, GS (glutamine synthetase) inhibitors or PPO (protoporphyrinogen-oxidase) inhibitors) as a result of conventional methods of breeding or genetic engineering. An example of a crop that has been rendered tolerant to imidazolinones, e.g. imazamox, by conventional methods of breeding (mutagenesis) is Clearfield® summer rape (Canola). Examples of crops that have been rendered tolerant to herbicides or classes of herbicides by genetic engineering methods include glyphosate- and glufosinate-resistant maize varieties commercially available under the trade names RoundupReady®, Herculex I® and LibertyLink®. 
     The term “useful plants” is to be understood as including also useful plants which have been so transformed by the use of recombinant DNA techniques that they are capable of synthesising one or more selectively acting toxins, such as are known, for example, from toxin-producing bacteria, especially those of the genus  Bacillus.    
     The term “useful plants” is to be understood as including also useful plants which have been so transformed by the use of recombinant DNA techniques that they are capable of synthesising antipathogenic substances having a selective action, such as, for example, the so-called “pathogenesis-related proteins” (PRPs, see e.g. EP-A-0 392 225). Examples of such antipathogenic substances and transgenic plants capable of synthesising such antipathogenic substances are known, for example, from EP-A-0 392 225, WO 95/33818, and EP-A-0 353 191. The methods of producing such transgenic plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above. 
     The term “locus” of a useful plant as used herein is intended to embrace the place on which the useful plants are growing, where the plant propagation materials of the useful plants are sown or where the plant propagation materials of the useful plants will be placed into the soil. An example for such a locus is a field, on which crop plants are growing. 
     The term “plant propagation material” is understood to denote generative parts of the plant, such as seeds, which can be used for the multiplication of the latter, and vegetative material, such as cuttings or tubers, for example potatoes. There may be mentioned for example seeds (in the strict sense), roots, fruits, tubers, bulbs, rhizomes and parts of plants. Germinated plants and young plants which are to be transplanted after germination or after emergence from the soil, may also be mentioned. These young plants may be protected before transplantation by a total or partial treatment by immersion. Preferably “plant propagation material” is understood to denote seeds. 
     The compositions of the present invention may also be used in the field of protecting storage goods against attack of fungi. According to the present invention, the term “storage goods” is understood to denote natural substances of vegetable and/or animal origin and their processed forms, which have been taken from the natural life cycle and for which long-term protection is desired. Storage goods of vegetable origin, such as plants or parts thereof, for example stalks, leafs, tubers, seeds, fruits or grains, can be protected in the freshly harvested state or in processed form, such as pre-dried, moistened, comminuted, ground, pressed or roasted. Also falling under the definition of storage goods is timber, whether in the form of crude timber, such as construction timber, electricity pylons and barriers, or in the form of finished articles, such as furniture or objects made from wood. Storage goods of animal origin are hides, leather, furs, hairs and the like. The compositions according the present invention can prevent disadvantageous effects such as decay, discoloration or mold. Preferably “storage goods” is understood to denote natural substances of vegetable origin and/or their processed forms, more preferably fruits and their processed forms, such as pomes, stone fruits, soft fruits and citrus fruits and their processed forms. In another preferred embodiment of the invention “storage goods” is understood to denote wood. 
     Therefore a further aspect of the present invention is a method of protecting storage goods, which comprises applying to the storage goods a composition according to the invention. 
     The compositions of the present invention may also be used in the field of protecting technical material against attack of fungi. According to the present invention, the term “technical material” includes paper; carpets; constructions; cooling and heating systems; wall-boards; ventilation and air conditioning systems and the like; preferably “technical material” is understood to denote wall-boards. The compositions according the present invention can prevent disadvantageous effects such as decay, discoloration or mold. 
     The compositions according to the invention are particularly effective against powdery mildews; rusts; leafspot species; early blights and molds; especially against  Septoria, Puccinia, Erysiphe, Pyrenophora  and  Tapesia  in cereals;  Phakopsora  in soybeans;  Hemileia  in coffee;  Phragmidium  in roses;  Alternaria  in potatoes, tomatoes and cucurbits;  Sclerotinia  in turf, vegetables, sunflower and oil seed rape; black rot, red fire, powdery mildew, grey mold and dead arm disease in vine;  Botrytis cinerea  in fruits;  Monilinia  spp. in fruits and  Penicillium  spp. in fruits. 
     The compositions according to the invention are furthermore particularly effective against seedborne and soilborne diseases, such as  Alternaria  spp.,  Ascochyta  spp.,  Botrytis cinerea, Cercospora  spp.,  Claviceps purpurea, Cochliobolus sativus, Colletotrichum  spp.,  Epicoccum  spp.,  Fusarium graminearum, Fusarium moniliforme, Fusarium oxysporum, Fusarium proliferatum, Fusarium solani, Fusarium subglutinans, Gaumannomyces graminis, Helminthosporium  spp.,  Microdochium nivale, Phoma  spp.,  Pyrenophora graminea, Pyricularia oryzae, Rhizoctonia solani, Rhizoctonia cerealis, Sclerotinia  spp.,  Septoria  spp.,  Sphacelotheca reilliana, Tilletia  spp.,  Typhula incarnata, Urocystis occulta, Ustilago  spp. or  Verticillium  spp.; in particular against pathogens of cereals, such as wheat, barley, rye or oats; maize; rice; cotton; soybean; turf; sugarbeet; oil seed rape; potatoes; pulse crops, such as peas, lentils or chickpea; and sunflower. 
     The compositions according to the invention are furthermore particularly effective against post harvest diseases such as  Botrytis cinerea, Colletotrichum musae, Curvularia lunata, Fusarium semitecum, Geotrichum candidum, Monilinia fructicola, Monilinia fructigena, Monilinia laxa, Mucor piriformis, Penicilium italicum, Penicilium solitum, Penicillium digitatum  or  Penicillium expansum  in particular against pathogens of fruits, such as pomefruits, for example apples and pears, stone fruits, for example peaches and plums, citrus, melons, papaya, kiwi, mango, berries, for example strawberries, avocados, pomegranates and bananas, and nuts. 
     The compositions according to the invention are particularly useful for controlling the following diseases on the following crops: 
       Alternaria  species in fruit and vegetables;  Ascochyta  species in pulse crops;  Botrytis cinerea  in strawberries, tomatoes, sunflower, pulse crops, vegetables and grapes, such as  Botrytis cinerea  on grape;  Cercospora arachidicola  in peanuts;  Cochliobolus sativus  in cereals;  Colletotrichum  species in pulse crops;  Erysiphe  species in cereals; such as  Erysiphe graminis  on wheat and  Erysiphe graminis  on barley;  Erysiphe cichoracearum  and  Sphaerotheca fuliginea  in cucurbits;  Fusarium  species in cereals and maize;  Gäumannomyces graminis  in cereals and lawns;  Helminthosporium  species in maize, rice and potatoes;  Hemileia vastatrix  on coffee;  Microdochium  species in wheat and rye;  Mycosphaerella fijiensis  in banana;  Phakopsora  species in soybeans, such as  Phakopsora pachyrizi  in soybeans;  Puccinia  species in cereals, broadleaf crops and perennial plants; such as  Puccinia recondita  on wheat,  Puccinia striiformis  on wheat and  Puccinia recondita  on barley;  Pseudocercosporella  species in cereals, such as  Pseudocercosporella herpotrichoides  in wheat;  Phragmidium mucronatum  in roses;  Podosphaera  species in fruits;  Pyrenophora  species in barley, such as  Pyrenophora teres  on barley;  Pyricularia oryzae  in rice;  Ramularia collo - cygni  in barley;  Rhizoctonia  species in cotton, soybean, cereals, maize, potatoes, rice and lawns, such as  Rhizoctonia solani  on potato, rice, turf and cotton;  Rhynchosporium secalis  on barley,  Rhynchosporium secalis  on rye;  Sclerotinia  species in lawns, lettuce, vegetables and oil seed rape, such as  Sclerotinia sclerotiorum  on oilseed rape and  Sclerotinia homeocarpa  on turf;  Septoria  species in cereals, soybean and vegetables, such as  Septoria tritici  on wheat,  Septoria nodorum  on wheat and  Septoria  glycines on soybean;  Sphacelotheca reilliana  in maize;  Tilletia  species in cereals;  Uncinula necator, Guignardia bidwellii  and  Phomopsis viticola  in vines;  Urocystis occulta  in rye;  Uromyces  species in beans;  Ustilago  species in cereals and maize;  Venturia  species in fruits, such as  Venturia inequalis  on apple;  Monilinia  species on fruits;  Penicillium  species on citrus and apples. 
     In general, the weight ratio of component (A) to component (B) is from 2000:1 to 1:1000. A non-limiting example for such weight ratios is compound of formula I: compound of formula B-2 is 10:1. The weight ratio of component (A) to component (B) is preferably from 100:1 to 1:100; more preferably from 20:1 to 1:50. 
     It has been found, surprisingly, that certain weight ratios of component (A) to component (B) are able to give rise to synergistic activity. Therefore, a further aspect of the invention are compositions, wherein component (A) and component (B) are present in the composition in amounts producing a synergistic effect. This synergistic activity is apparent from the fact that the fungicidal activity of the composition comprising component (A) and component (B) is greater than the sum of the fungicidal activities of component (A) and of component (B). This synergistic activity extends the range of action of component (A) and component (B) in two ways. Firstly, the rates of application of component (A) and component (B) are lowered whilst the action remains equally good, meaning that the active ingredient mixture still achieves a high degree of phytopathogen control even where the two individual components have become totally ineffective in such a low application rate range. Secondly, there is a substantial broadening of the spectrum of phytopathogens that can be controlled. 
     However, besides the actual synergistic action with respect to fungicidal activity, the compositions according to the invention can also have further surprising advantageous properties. Examples of such advantageous properties that may be mentioned are: more advantageuos degradability; improved toxicological and/or ecotoxicological behaviour; or improved characteristics of the useful plants including: emergence, crop yields, more developed root system, tillering increase, increase in plant height, bigger leaf blade, less dead basal leaves, stronger tillers, greener leaf colour, less fertilizers needed, less seeds needed, more productive tillers, earlier flowering, early grain maturity, less plant verse (lodging), increased shoot growth, improved plant vigor, and early germination. 
     Some compositions according to the invention have a systemic action and can be used as foliar, soil and seed treatment fungicides. 
     With the compositions according to the invention it is possible to inhibit or destroy the phytopathogenic microorganisms which occur in plants or in parts of plants (fruit, blossoms, leaves, stems, tubers, roots) in different useful plants, while at the same time the parts of plants which grow later are also protected from attack by phytopathogenic microorganisms. 
     The compositions according to the invention can be applied to the phytopathogenic microorganisms, the useful plants, the locus thereof, the propagation material thereof, storage goods or technical materials threatened by microorganism attack. 
     The compositions according to the invention may be applied before or after infection of the useful plants, the propagation material thereof, storage goods or technical materials by the microorganisms. 
     The amount of a composition according to the invention to be applied, will depend on various factors, such as the compounds employed; the subject of the treatment, such as, for example plants, soil or seeds; the type of treatment, such as, for example spraying, dusting or seed dressing; the purpose of the treatment, such as, for example prophylactic or therapeutic; the type of fungi to be controlled or the application time. 
     When applied to the useful plants component (A) is typically applied at a rate of 5 to 2000 g a.i./ha, particularly 10 to 1000 g a.i./ha, e.g. 50, 75, 100 or 200 g a.i./ha, typically in association with 1 to 5000 g a.i./ha, particularly 2 to 2000 g a.i./ha, e.g. 100, 250, 500, 800, 1000, 1500 g a.i./ha of component (B). 
     In agricultural practice the application rates of the compositions according to the invention depend on the type of effect desired, and typically range from 20 to 4000 g of total composition per hectare. 
     When the compositions according to the invention are used for treating seed, rates of 0.001 to 50 g of a compound of component (A) per kg of seed, preferably from 0.01 to log per kg of seed, and 0.001 to 50 g of a compound of component (B), per kg of seed, preferably from 0.01 to 10 g per kg of seed, are generally sufficient. 
     The composition of the invention may be employed in any conventional form, for example in the form of a twin pack, a powder for dry seed treatment (DS), an emulsion for seed treatment (ES), a flowable concentrate for seed treatment (FS), a solution for seed treatment (LS), a water dispersible powder for seed treatment (WS), a capsule suspension for seed treatment (CF), a gel for seed treatment (GF), an emulsion concentrate (EC), a suspension concentrate (SC), a suspo-emulsion (SE), a capsule suspension (CS), a water dispersible granule (WG), an emulsifiable granule (EG), an emulsion, water in oil (EO), an emulsion, oil in water (EW), a micro-emulsion (ME), an oil dispersion (OD), an oil miscible flowable (OF), an oil miscible liquid (OL), a soluble concentrate (SL), an ultra-low volume suspension (SU), an ultra-low volume liquid (UL), a technical concentrate (TK), a dispersible concentrate (DC), a wettable powder (WP) or any technically feasible formulation in combination with agriculturally acceptable adjuvants. 
     Such compositions may be produced in conventional manner, e.g. by mixing the active ingredients with at least one appropriate inert formulation adjuvant (for example, diluents, solvents, fillers and optionally other formulating ingredients such as surfactants, biocides, anti-freeze, stickers, thickeners and compounds that provide adjuvancy effects). Also conventional slow release formulations may be employed where long lasting efficacy is intended. Particularly formulations to be applied in spraying forms, such as water dispersible concentrates (e.g. EC, SC, DC, OD, SE, EW, EO and the like), wettable powders and granules, may contain surfactants such as wetting and dispersing agents and other compounds that provide adjuvancy effects, e.g. the condensation product of formaldehyde with naphthalene sulphonate, an alkylarylsulphonate, a lignin sulphonate, a fatty alkyl sulphate, and ethoxylated alkylphenol and an ethoxylated fatty alcohol. 
     The compositions according to the invention may also comprise further pesticides, such as, for example, fungicides, insecticides or herbicides. 
     A seed dressing formulation is applied in a manner known per se to the seeds employing the compositions according to the invention and a diluent in suitable seed dressing formulation form, e.g. as an aqueous suspension or in a dry powder form having good adherence to the seeds. Such seed dressing formulations are known in the art. Seed dressing formulations may contain the single active ingredients or the combination of active ingredients in encapsulated form, e.g. as slow release capsules or microcapsules. 
     In general, the formulations include from 0.01 to 90% by weight of active agent, from 0 to 20% agriculturally acceptable surfactant and 10 to 99.99% solid or liquid formulation inerts and adjuvant(s), the active agent consisting of at least a compound of component (A) together with a compound of component (B), and optionally other active agents, particularly microbiocides or conservatives or the like. Concentrated forms of compositions generally contain in between about 2 and 80%, preferably between about 5 and 70% by weight of active agent. Application forms of formulation may for example contain from 0.01 to 20% by weight, preferably from 0.01 to 5% by weight of active agent. Whereas commercial products will preferably be formulated as concentrates, the end user will normally employ diluted formulations. 
     The Examples which follow serve to illustrate the invention, “active ingredient” denoting a mixture of component (A) and component (B) in a specific mixing ratio. 
     Formulation Examples 
       
     
       
         
           
               
               
               
               
             
               
                   
                   
               
               
                   
                 Wettable powders 
                 a) 
                 b) 
               
               
                   
                   
               
             
            
               
                   
                 active ingredient [A):B) = 1:3(a), 1:1(b)] 
                 25%  
                 75% 
               
               
                   
                 sodium lignosulfonate 
                 5% 
                 — 
               
               
                   
                 sodium lauryl sulfate 
                 3% 
                  5% 
               
               
                   
                 sodium diisobutylnaphthalenesulfonate 
                 — 
                 10% 
               
               
                   
                 (7-8 mol of ethylene oxide) 
               
               
                   
                 highly dispersed silicic acid 
                 5% 
                 10% 
               
               
                   
                 kaolin 
                 62%  
                 — 
               
               
                   
                   
               
            
           
         
       
     
     The active ingredient is thoroughly mixed with the other formulation components and the mixture is thoroughly ground in a suitable mill, affording wettable powders that can be diluted with water to give suspensions of the desired concentration. 
     
       
         
           
               
               
               
               
             
               
                   
                   
               
               
                   
                 Powders for dry seed treatment 
                 a) 
                 b) 
               
               
                   
                   
               
             
            
               
                   
                 active ingredient [A):B) = 1:3(a), 1:1(b)] 
                 25% 
                 75% 
               
               
                   
                 light mineral oil 
                  5% 
                  5% 
               
               
                   
                 highly dispersed silicic acid 
                  5% 
                 — 
               
               
                   
                 kaolin 
                 65% 
                 — 
               
               
                   
                 talc 
                 — 
                 20 
               
               
                   
                   
               
            
           
         
       
     
     The active ingredient is thoroughly mixed with the other formulation components and the mixture is thoroughly ground in a suitable mill, affording powders that can be used directly for seed treatment. 
     
       
         
           
               
               
               
             
               
                   
                   
               
               
                   
                 Emulsifiable concentrate 
               
               
                   
                   
               
             
            
               
                   
               
            
           
           
               
               
               
            
               
                   
                 active ingredient (A):B) = 1:6) 
                 10% 
               
               
                   
                 octylphenol polyethylene glycol ether 
                 3% 
               
               
                   
                 (4-5 mol of ethylene oxide) 
               
               
                   
                 calcium dodecylbenzenesulfonate 
                 3% 
               
               
                   
                 castor oil polyglycol ether (35 mol of ethylene oxide) 
                 4% 
               
               
                   
                 cyclohexanone 
                 30% 
               
               
                   
                 xylene mixture 
                 50% 
               
               
                   
                   
               
            
           
         
       
     
     Emulsions of any required dilution, which can be used in plant protection, can be obtained from this concentrate by dilution with water. 
     
       
         
           
               
               
               
               
             
               
                   
                   
               
               
                   
                 Dustable powders 
                 a) 
                 b) 
               
               
                   
                   
               
             
            
               
                   
                 active ingredient [A):B) = 1:6(a), 1:10(b)] 
                  5% 
                  6% 
               
               
                   
                 talcum 
                 95% 
                 — 
               
               
                   
                 kaolin 
                 — 
                 94% 
               
               
                   
                   
               
            
           
         
       
     
     Ready-for-use dusts are obtained by mixing the active ingredient with the carriers and grinding the mixture in a suitable mill. Such powders can also be used for dry dressings for seed. 
     
       
         
           
               
               
               
             
               
                   
                   
               
               
                   
                 Extruded granules 
                 % w/w 
               
               
                   
                   
               
             
            
               
                   
               
            
           
           
               
               
               
            
               
                   
                 active ingredient (A):B) = 2:1) 
                 15% 
               
               
                   
                 sodium lignosulfonate 
                 2% 
               
               
                   
                 sodium alkyl naphthalene sulfonate 
                 1% 
               
               
                   
                 kaolin 
                 82% 
               
               
                   
                   
               
            
           
         
       
     
     The active ingredient is mixed and ground with the other formulation components, and the mixture is moistened with water. The mixture is extruded and then dried in a stream of air. 
     
       
         
           
               
               
             
               
                   
               
               
                 Suspension concentrate 
               
               
                   
               
             
            
               
                   
               
            
           
           
               
               
            
               
                 active ingredient (A):B) = 1:8) 
                 40% 
               
               
                 propylene glycol 
                 10% 
               
               
                 nonylphenol polyethylene glycol ether (15 mol of ethylene oxide) 
                 6% 
               
               
                 sodium lignosulfonate 
                 10% 
               
               
                 carboxymethylcellulose 
                 1% 
               
               
                 silicone oil (in the form of a 75% emulsion in water) 
                 1% 
               
               
                 water 
                 32% 
               
               
                   
               
            
           
         
       
     
     The finely ground active ingredient is intimately mixed with the other formulation components, giving a suspension concentrate which can be diluted in water at any desired rate. Using such dilutions, living plants as well as plant propagation material can be treated and protected against infestation by microorganisms, by spraying, pouring or immersion. 
     
       
         
           
               
               
               
             
               
                   
                   
               
               
                   
                 Flowable concentrate for seed treatment 
               
               
                   
                   
               
             
            
               
                   
                 active ingredient (A):B) = 1:8) 
                 40%  
               
               
                   
                 propylene glycol 
                 5% 
               
               
                   
                 copolymer butanol PO/EO 
                 2% 
               
               
                   
                 tristyrenephenole ethoxylate (with 10-20 moles EO) 
                 2% 
               
               
                   
                 1,2-benzisothiazolin-3-one 
                 0.5%   
               
               
                   
                 monoazo-pigment calcium salt 
                 5% 
               
               
                   
                 silicone oil (in the form of a 75% emulsion in water) 
                 0.2%   
               
               
                   
                 water 
                 45.3%   
               
               
                   
                   
               
            
           
         
       
     
     The finely ground active ingredient is intimately mixed with the other formulation components, giving a suspension concentrate which can be diluted further in water to be applied to seeds. Using such dilutions, propagation material can be treated and protected against infestation by microorganisms, by spraying, pouring or immersion. 
     Slow Release Capsule Suspension 
     28 parts of a combination of a compound of component (A) and a compound of component (B), or of each of these compounds separately, are mixed with 2 parts of an aromatic solvent and 7 parts of toluene diisocyanate/polymethylene-polyphenylisocyanate-mixture (8:1). This mixture is emulsified in a mixture of 1.2 parts of polyvinylalcohol, 0.05 parts of a defoamer and 51.6 parts of water until the desired particle size is achieved. To this emulsion a mixture of 2.8 parts 1,6-diaminohexane in 5.3 parts of water is added. The mixture is agitated until the polymerization reaction is completed. 
     The obtained capsule suspension is stabilized by adding 0.25 parts of a thickener and 3 parts of a dispersing agent. The capsule suspension formulation contains 28% of the active ingredients. The median capsule diameter is 8-15 microns. The resulting formulation is applied to seeds as an aqueous suspension in an apparatus suitable for that purpose. 
     Biological Examples 
     A synergistic effect exists whenever the action of an active ingredient combination is greater than the sum of the actions of the individual components. 
     The action to be expected E for a given active ingredient combination obeys the so-called COLBY formula and can be calculated as follows (COLBY, S. R. “Calculating synergistic and antagonistic responses of herbicide combination”. Weeds, Vol. 15, pages 20-22; 1967): 
     ppm=milligrams of active ingredient (=a.i.) per liter of spray mixture
 
X=% action by active ingredient A) using p ppm of active ingredient
 
Y=% action by active ingredient B) using q ppm of active ingredient.
 
     According to COLBY, the expected (additive) action of active ingredients A)+B) using p+q ppm of active ingredient is 
     
       
         
           
             E 
             = 
             
               X 
               + 
               Y 
               - 
               
                 
                   X 
                   · 
                   Y 
                 
                 100 
               
             
           
         
       
     
     If the action actually observed (O) is greater than the expected action (E), then the action of the combination is super-additive, i.e. there is a synergistic effect. In mathematical terms, synergism corresponds to a positive value for the difference of (O-E). In the case of purely complementary addition of activities (expected activity), said difference (O-E) is zero. A negative value of said difference (O-E) signals a loss of activity compared to the expected activity. 
     In the following examples a specific compound of formula (I) was used. Said compound of formula (I) was a mixture of the racemic syn- and anti-compound of formula (I), in a syn/anti-ratio of 9:1. 
     Example B-1 
     Action Against  Septoria tritici    
     Conidia of the fungus from cryogenic storage are directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of the test compounds into a microtiter plate (96-well format) the nutrient broth containing the fungal spores is added. The test plates are incubated at 24° C. and the inhibition of growth is determined photometrically after 72 hrs. The fungicide interactions in the combinations are calculated according to COLBY method. 
     
       
         
           
               
            
               
                   
               
               
                 Dosage in mg active ingredient/liter final medium 
               
            
           
           
               
               
               
               
            
               
                 Cpd I in 
                 Cpd B-1.1 
                 Expected control in % 
                 Observed control in % 
               
               
                 ppm 
                 in ppm 
                 (% C exp ) 
                 (% C obs ) 
               
               
                 [mg/L] 
                 [mg/L] 
                 expected 
                 observed 
               
               
                   
               
            
           
           
               
               
               
               
            
               
                 0.063 
                 — 
                 — 
                 26 
               
               
                 0.125 
                 — 
                 — 
                 52 
               
               
                 — 
                 0.063 
                 — 
                 6 
               
               
                 — 
                 0.125 
                 — 
                 0 
               
               
                 0.063 
                 0.063 
                 31 
                 38 
               
               
                 0.125 
                 0.125 
                 52 
                 62 
               
               
                   
               
            
           
         
       
     
     Example B-2 
     Action Against  Pseudocercosporella herpotrichoides  var.  acuformis  (Evespot/Cereals) 
     Conidia of the fungus from cryogenic storage are directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of the test compounds into a microtiter plate (96-well format) the nutrient broth containing the fungal spores is added. The test plates are incubated at 24° C. and the inhibition of growth is determined photometrically after 72 hrs. The fungicide interactions in the combinations are calculated according to COLBY method. 
     
       
         
           
               
            
               
                   
               
               
                 Dosage in mg active ingredient/liter final medium 
               
            
           
           
               
               
               
               
            
               
                 Cpd I in 
                 Cpd B-1.1 
                 Expected control in % 
                 Observed control in % 
               
               
                 ppm 
                 in ppm 
                 (% C exp ) 
                 (% C obs ) 
               
               
                 [mg/L] 
                 [mg/L] 
                 expected 
                 observed 
               
               
                   
               
            
           
           
               
               
               
               
            
               
                 0.016 
                 — 
                 — 
                 12 
               
               
                 0.031 
                 — 
                 — 
                 40 
               
               
                 0.063 
                 — 
                 — 
                 67 
               
               
                 — 
                 0.016 
                 — 
                 1 
               
               
                 — 
                 0.031 
                 — 
                 3 
               
               
                 — 
                 0.063 
                 — 
                 14 
               
               
                 0.016 
                 0.016 
                 13 
                 18 
               
               
                 0.031 
                 0.031 
                 42 
                 54 
               
               
                 0.063 
                 0.063 
                 72 
                 78