BE537873A - - Google Patents

Description

       

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   The present invention relates generally to insecticidal compositions and more especially to insecticidal compositions containing organic derivatives of arbamic acid and organic compounds containing phosphorus, the insecticidal efficacy of each. part of the composition being hereby increased on the other, to achieve an unexpected combined effect often referred to as a synergistic effect.



   When a combination of two or more materials has an activity higher than the expected activity, for example an insecticidal activity, the phenomenon is called synergism. The mechanism of synergism is not understood. It is in fact very likely that it differs depending on the synergistic combinations. The term "synergism" can however be defined as a cooperative action which occurs in combinations of two or more elements with biological activity and in which the combined activity of the two elements is greater than the sum of the activities of these elements used separately. The insecticidal activity of the two mixed elements cannot be predicted from the known values of the individual elements, but is unexpected and does not depend on the individual activity of either of the two.

   However, within certain narrow limits of parent compound classes by structure, the existence of synergistic activity could be predicted.



   Certain phosphates, thiophosphates and similar organic phosphorus compounds are known and used as insecticides for homes, gardens, truck crops, forages and to destroy orchard insects. It is highly desirable to increase both the stun ability and the insect killing ability of these phosphate compounds in insecticidal compositions. Hitherto, compounds which exert a synergistic action with insecticides containing phosphorus could not be used under a wide variety of conditions and against a large number of different species of insects.



   An aim of the present invention is to provide insecticidal compositions having better killing capacity.



   Another object is to provide novel compositions containing compounds capable of exerting a synergistic action on the properties of stunning and killing insects of toxic insecticidal agents.



   Another object is to provide insecticidal compositions containing organic phosphorus compounds and esters of the carbamate type, the combination of which causes synergistic effects for the two classes of compounds.



   Another object of the invention is to provide compositions comprising the relatively toxic insecticides containing phosphorus, where superior insecticidal activity is obtained by a synergistic effect, but where the final toxicity to warm-blooded animals is greatly reduced due to the lower concentrations of phosphorus compounds needed when used in combination with the relatively less toxic carbamates.



   Other objects and advantages of the invention will emerge from the remainder of the description.



   It has been found that compounds of the class of organic phosphorus derivatives containing acids and certain selected organic carbamates exert surprising and unexpected synergistic action when used in combinations.



   The organic element containing phosphorus of syner-

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   -mall be generally defined by the following formula;
 EMI2.1
 In this formula, X is an oxygen or sulfur atom, R1 and are alkoxy groups like methoxy, ethoxy or isopropoxy, or dialkylamino groups like dimethylamino and R1 and R2 can be the same or different and R3 is a radical which can be aryl or substituted aryl, such as phenyl, nitrophenyl or nitrochlorophenyl, heterocyclic such as pyrimidyl or ooumaryl, or substituted pyrimidyl or substituted coumaryl, alkyl or substituted alkyl, such as diethyl-to-alpha-siocinyl, or other phosphorus-containing radicals such as
 EMI2.2
 where R1, R2 and X are taken in the sense indicated above.



   The compounds of this class are in particular 0,0-diethyl-0- (4-
 EMI2.3
 nitrophenyl) thiophosphate (Parathion), 0,0-dimethyl-o- (4-nitrophenyl) thiophosphate (Methyl-Parathion), 0,0-dimethyl-0- (3-ohloro-4-nitrophenyl) thiophosphate (Chlorothion) , 0,0-dimethyl-0- (2-chloro-4-nitrophenyl) thiophosphate (C-4124), 0,0-diethyl-0- (7- 3-ohloro-4-methyl-ooumaryl)) thiophosphate (B-21/199), 0,0-dimethyl-o- (7- (3-chloro-q.-methyloumaryl?) Thiophosphate (B-21/200), 0,0-diethyl-0- ( 7- (4-methylcoumaryl)) thiophosphate (Potasan, 0,0-diethyl-0- (2- (4-isopiopyl-6-methylpyiimidyll ') thiophosphate (Diazinon), 0.0-dimethyl-S- (1,2 -dicarbethoxyethyl) dithiophosphate (Halathion, tetraethyl-dithiopyrophosphate (Sülfotepp), tetraethyl-pyrophosphate (TEPP), and ltoctamethyl-pyrophosphoramide (Schradan)

  . The particulars in parentheses are either trade names or code numbers and are included to facilitate later mentions of these chemicals.



   In general, the compounds listed above are organic derivatives of acids containing phosphorus, and more especially these insecticidal compounds can be considered as organic esters or amides of phosphoric acid, thiophosphoric acid, dithiophosphoric acid, pyrophosphoric acid and dithionopyrophosphoric acid.



   The carbamates useful as elements of these compositions can be defined by the following general formula:
 EMI2.4
 
In this formula, R4 and R5 can be the same or different and are hydrogen, an alkyl group such as methyl, ethyl, isopropyl,
 EMI2.5
 o-propyl, n-butyl, tent.

   -butyl, 2-ethyl-hexyl, dodecyl, etc., a

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 substituted alkyl group like 2-chloroethyl, 2- (1-chloropropyl), 3-methoxypropyl etc ... aryl group like phenyl or naphthyl, substituted aryl group like chlorophenyl, nitrophenyl, methoxyphenyl, methylphenyl and analogous polysubstituted phenyl radicals, a alkenyl group such as vinyl, allyl, butenyl, undecylenyl etc., a heterocyclic group such as furfuryl, thienyl, pyridyl, pyrazolyl, pyrimidyl, thiazolyl etc., or cycloalkyl, such as cyclopentyl, cyclohexyl etc., aralkyl such as benzyl or acyl such as acetyl and benzoyl.

   The atoms X1 and X2 can be oxygen, either both oxygen, one oxygen and the other sulfur, or both sulfur. R6 can be an alkyl group such as methyl, ethyl, isopropyl, n-propyl, n-butyl, tert.-butyl, 2-ethylhexyl, dodecyl etc. a substituted alkyl group such as 2-chloroethyl, 2- (1-chloropropyl), 3-metthoxypropyl etc. an aryl group such as phenyl or naphthyl, a substituted aryl group such as chlorophenyl, nitrophenyl, methoxyphenyl, methylphenyl and analogous polysubstituted phenyl radicals, an alkenyl group such as vinyl, allyl, butenyl, undecylenyl etc.

   a heterocyl group such as fur-furyl, thienyl, pyridyl, pyrazolyl, pyrimidyl, thiazolyl etc. or cycloalkyl such as cyclopentyl, cyclohexyl etc. or aralkyl such as benzyl.



   It has also been found that the carbamates useful as ingredients of these combinations can be defined by the following general formula:
 EMI3.1
   In this formula, M is a divalent alkyl or alkyloxy radical, for example pentamethylene, hexamethylene, ethylene-oxyethylene, etc.

   R6 can be an alkyl group such as methyl, ethyl, isopropyl, n-propyl, n-butyl, terto-butyl, 2-ethyl-hexyl, dodecyl, etc., substituted alkyl such as 2-chloroethyl, 2- (1-chloropopyl) , 3-methoxypropyl, etc., aryl such as phenyl or naphthyl, substituted aryl such as ohlorophenyl, nitrophenyl, methoxyphenyl, methylphenyl and similar polysubstituted phenyl radicals, alkenyl such as vinyl, allyl, butenyl, undecylenyl etc. heterocyclic such as furfuryl, thienyl, pyridyl, pyrazolyl, pyrimidyl, thiazolyl etc ,. or cycloalkyl such as cyolopentyl, cyclohexyl etc.

   or aralkyl such as benzyl,
For ease of reference in the nomenclature of these carbamates, the compounds in which R4 and R5 are hydrogen are hereinafter called “unsubstituted carbamates”; those in which only one of R4 or R5 is hydrogen will be referred to as "N-mono-substituted carbamates" and those in which neither R4 nor R5 is hydrogen are referred to as "N, N-disubstituted carbamates".



   Some of the carbamates included in this general class are unsubstituted carbamates like propyl-carbamate and phenyl-carbamate, monosubstituted carbamates like phenyl-N-methylcarbamate, phenyl-N-ethylcarbamate, 1-naphthyl- N-ethylcarbamate, 2-naphthyl-N-ethylcarbamate, phenyl-N-ethylthiocarbamate, phenyl-N-isopropylcarbamate, phenyl-N-butylcarbamate, phenyl-N-tert.

   -butylcarbamate, phenyl-N-dodecylcarbamate, phenyl-N-allylcarbamate, phenyl-N- cyolohexylcarbamate, phenyl-N-carbethoxymethylcarbamate, phenyl-N- (2-hydroxyethyl) carbamate, phenyl-N- (3 -methoxy) -propylcarbamate, phenyl-N-benzylcarbamate, phenyl-N-phenyl-carbamate, phenyl-N-phenyldithiocarbamate, phenyl-N- (2-chlorophenyl) -carbamate, phenyl-N- (4- chlorophenyl) -carbamate, phenyl-N- (4-hydroxyphenyl) -carbamate, phenyl-N- (1-naphthyl) -carbamate, phenyl-N- (2-naphthyl) -carbamate, pbe-

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 EMI4.1
 nyl-il-furfuiylcaibamate, 2-chlorophenyl-ethylcarbamate, 4-chlorophenyl-N-ethylcarbamate, 4-nitrophenyl-NL-ethylcarbamate, 3-methyl-phenyl-N-ethylcarbamate,

   3-methylphenyl-N-ethyl-thiolcarbamate, 4methylphenyl-N-ethylcarbamate, 4-methoxy-phenyl-N-ethylcarbamate,
 EMI4.2
 4-methylumbelliféionyl-1F-ethylcarb & mate, 3-chlorophenyl-N-isopropylcarbamate, benzyl-Iethylearbamate, ethyl-N-carbamate, ethyl-Itert.

   octylcarbamate, isopropyl-N-cyclohexylcarbamate, 2-ethyl-hexyl-N-ethylcarbamate, ethyl-N furfurylcarbamate, ethyl-N-phenylcarbamate ,, 2-ethylhexyl-N-phenyl-carbamate, benzyl-N -phenylcarbamate, piponyl-N-phenylcarbamate, ethyl-N- (4-nitrophenyl) -carbamate, isopropyl-N-
 EMI4.3
 (3-chlorophenyl) -carbamate, llisopropyl-N- (3-trifluoromethyl-phenyl) -carbamate, 2-ethylhexyl-1 (3-chlorophenyl) -carbamate, trichloroethyl-Nphenylcarbamate, 2- (1-chloiopiopyl) - Ih-phenylcarbamate, ethyl-N-furfurylcarbamate, ben-, yl-N-furfuryl-carbamçate, isopropyl-N-benzoylcarcarbamate, cyolohexyl # N-éthylcar'bamate, allyl-N-phenylcarbamate, yl-N-ethylcarbamate, 2-naphthyl-Iethylcarbamate,

   and benzyl-Nphenylcarbamate and disubstituted carbamates such as phenyl-N, N-dimethylcarbamate, phenyl-N, N-diethβ.tcaiibaJiat: e "phenyl-1f, di -:.: .- propylcarbamate, pIlên.yl -B-methyl # N-ph.ényIoar'bamate, 3-chlorophenyl-N, N-dimethylcarbamate, 4-chlorophenyl-NN-dimethylcarbamate, phenyl-N, N-diethylthionocarbamate, ethyl-N, N- diisopropylcarbamate, 1 'ethyl # E', N-diphenylcarbamate, 1 'isopropyl-N-methyl-N-phenylcarbamate llisopropyl-N-methyl-N- (3-chlorophenyl) -carbamate, allyl-N-methyl-N- (3-ohlorophenyl) -carbamate, "phenyl-lpyrrolidinyl-carbamate" (N-carbophenoxypyrrolidine), "phenyl-N-piperidinyl-carbamate" (N-carbophenoxypiperidine), and "phenyl-N-morpholinylcarbamate" ( N-carbophenoxymorpholine).



   The phenyl esters of N-mono-substituted carbamic acids are particularly useful as ingredients of such compositions and may be defined by the general formula
 EMI4.4
 In this formula, R4 can be any alkyl radical having from 1 to 18 carbon atoms, a substituted alkyl radical, an aryl radical, a substituted aryl radical or a heterocyclic radical. In this group, the phenyl radical present as alcohol residue is substituted only by hydrogen atoms.



   The carbamates of this general class are monosubstituted phenyl esters such as phenyl-N-methylcarbamate, phenyl-N-ethyl-
 EMI4.5
 carbamate, phenyl-1,; - isopropylcarbamate, phenyl-Nn-butyloarbamate, phenyl-N -.- butylcarbamate, phenyl-N-dodecylcarbamate, phenyl-N-allylcarbamate, phenyl-N-cyolohexylcarbamate, phenyl-I-carbethoxymethylcarbamate, phenyl-I (2-hydroçyethyl) -carbamate, phenyl-N- (3-methoxy-propyl) -carbamate, phenyl-N-benzylcarbamate, phenyl-Nphenylcarbamate, phenyi-I ( 2-ehlorophenyl) -carbamate, phenyl-N- (4chlorophenyl) -carbamate, phenyl-N- (4-hydroxyphenyl) -carbamate, phenyl-N- (l, naphthyl) -carbamate, phenyl-N- ( 2-naphthyl) -oarbamate and phenyl-N-furfurylcarbamate.



   The substituted phenyl esters of N-monosubstituted carbamic acids particularly useful as ingredients of the above compositions can be defined by the formula

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 EMI5.1
 In this formula R4 can be any alkyl radical having from 1 to 18 carbon atoms, a substituted alkyl radical, an aryl radical, a substituted aryl radical or a heterocyclic radical and R7 can be a chlorine atom, a mitro group -, an alkoxy radical or an alkyl radical.



   The carbamates of this general class are N-monosubstituted phenyl esters such as 2-chlorophenyl-N-ethyl-carbamate, 4-
 EMI5.2
 chlorophenyl-N-ethylcarbamate, 4-nitrophenyl-ethylcarbamate, 3methylphenyl-N-ethylcarbamate, 4-methylphenyl-ethyloarbamate, 4methoxyphenyl-N-ethylcarbamate and 3-chlorophenyl-1-isopropyl.



   The alkyl esters of N-monosubstituted carbamic acids particularly useful as ingredients of these compositions can be defined by the general formula
 EMI5.3
   In this formula, R4 can be a cycloalkyl, phenyl, alkyl, phenyl, substituted, heterocyclic or acyl radical and R can be an alkyl radical having 1 to 12 carbon atoms.



   The carbamates included in this group are N-monosubstituted alkyl esters such as ethyl-N-tert.-octylcarbamate, isopropyl-N-oy-
 EMI5.4
 olohexylcarbamate, 2-ethylhexyl-N-ethyl-carbamate, ethyl-N-fiarfurylcarbamate, ethyl-Iphenylcarbamate, 2-ethylhexyl-N-phenylcarbamate, ethyl-N- (4-nitrophënyl) - carbamate, isopropyl-N- (3-ohlorophenyl) -oarbamate, isopropyl-N- (3-trifluorometh.ylphenyl) -carbamate, 2-ethylhexyl-N- (3-ohlorophenyl) -carbamate and '1' isopropyl-N-benzoyIcarbamate.



  Particularly useful N-monosubstituted carbamic substituted alkyl esters as ingredients for the above compositions are, for example tr3chlorethyl-lphenylcar'bamate and 2- (1-ahloropropyl) -N-phenylaarbamateo.
Particular examples of other types of N-monosubstituted carbamic acid esters which are particularly useful, but not shown
 EMI5.5
 felt in the above groups are:

   lta1lyl-N-phenyl-uarbamate, furfuryl-N-ethylcarbamate, 1-naphthyl-N-ethylcarbamate, 2-naphthyl-N-ethylcarbamate, benzyl-Itethyl = carbamate, benzyl-N-pheny # c rbmmàt, cyclohexyl-R9-ethylcarbamate, 4-methyl-umbelliferonyl-N-ethylcarbamate, piperonyl-N-phenyl-carbamate, phenyl-1V-ethylthiocar'bamate, 3-methyl-phenyl-N-ethylthiocarbamiocarbamate and phenyldithyl- you.



   Some of the esters of the N, N-disubstituted carbamic acids which are particularly useful as ingredients of these compositions are
 EMI5.6
 phenyl-N, N-dimethylcarbamate, phenyl-N, lS-diethylaarbamate, phenyl-N, N-di (n-propylcarbamate, phenyl-N-methyl-N-phenylcarbamate, 3-ahlorophenyl-N, R9 -dimethylaarbamate, 4-chlorophenyl-N, N-dimethylcarbamate, phenyl-N, N-diethyl-thionocarbamate, ethyl-N, N-diisopropylcarbamate, 1 ethyl-N, N-dipheylcarbamate, isopropyl-N- methyl-N-methyl-phenylcarbamate, isoprapyl-N-methyl-I (3-chlorophenyl) -carbamate, allyl-N-methyl-N- (3-chlorophenyl) -carbamate, "phenyl-N-pyrrolidinylcarbamate"

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 EMI6.1
 (N-carbophenoxypyrrolidine),

   "phenyl-N-piperidinylcarbamate (N-carbophenoypipérddin3) and" phenyl-N-morpholinylcarbamateil (N-carbophenoxymorpholine).



   Some of the carbamates described herein are believed to be new and hitherto unknown compounds and the present invention intends to claim them as such. Typical processes for their preparation are described in the following examples.



   The combinations of these compounds are not all equivalent from the point of view of synergistic effect, some combinations being much superior to others. However, each combination is significantly superior in insecticidal activity to the combined effect of the ingredients used alone as shown in the examples which follow.



   The synergistic combinations described above offer many advantages over the use of either of the two ingredients used separately as well as advantages over other combinations having less activity. For example, these combinations are advantageous in that they only require the use of much smaller amounts of relatively toxic insecticides containing phosphorus and therefore present seriously reduced risks in use, while at the same time. time they ensure even greater insecticidal efficacy.



   The remarkable insecticidal effects of the combination of carbamates and phosphorus-containing insecticides give unexpected advantages for the destruction of a wide variety of insects and spiders. The combinations are very effective and economical for large scale inseoticide applications such as insect control in truck crops, forages and orchards.



   Synergistic combinations of organic phosphates and organic carbamates can be presented in the form of aqueous emulsions, dry or wettable powders, solutions or in any other suitable vehicle. These insecticidal compositions can be used as a spray, dusting, aerosol, coatings and in the form of residues. In general, they can be applied by methods normally used for the control or destruction of insects, spiders, etc. Thus, these insecticidal compositions can enter into compositions with solvents, diluents and vehicles. , adhesion, spreading, wetting, and emulsifying agents and other ingredients.



   The relative proportions of the active ingredients as well as the vehicles, solvents, dispersants and other inert products can vary within wide limits.



   Thus, the relative proportion between the compound containing phosphorus and the carbamate can vary from 20 parts of the first for 1 part of the second to 1 part of the first for 40 parts of the second, and preferably from 5 parts of the first to 1. part of the second to 1 part of the second for 10 parts of the first.



   The amounts of the toxic ingredients in the final insecticidal compositions can vary from 0.01 to 25% for the phosphorus compound.
 EMI6.2
 phorus and 0.05 to 50% for the carbamate and preferably 0.1 to 10% for the phosphorus compound and 0.1 to 25% for the carbamate.



   The test methods are described below, The details of the experiments and in particular the type of composition and the mode of application or dosage and the species of insects which serve as subjects in the ex-

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 perienes are shown in the examples.



   The insects used in the tests are the house fly Musca domestica L.), the Mexican bean parasite (Mexican bean
 EMI7.1
 be-etle) lepilachna varivestis Nuls.), pea aphidian (Macrosiphum pisi LKltb.z, two-spotted spider (Tetranvchus bimaculatus Harvey), harlequin (harlequin bug) (Murgantia. histi'ionica LHahn¯7 and the pumpkin parasite (squash bug) (Anasa tristis).



   The test methods used are as follows:
SPRINKLING TOWER PROCESS.-
This process is described in J. Econ.Ent, 43, N 2, 188-190 (1950) by Moore.



   The sprinkling apparatus is a vertical glass cylinder 34 inches high (86 cm) and 8.5 inches in diameter (21.5 cm), into which the sample of powder is introduced through a small hole in the center of the lid using a laboratory sprinkler working under 40 psi (2.8 kg / cm2) air pressure. The sprinkling set comprises a 10 cc beaker in which the weighed sample is placed, provided with a rubber stopper through which pass the tubes for the air supply and the powder outlet, both copper and! inch in diameter (6mm). At the outer end of the air supply tube is a trigger valve which is used to regulate the powder feed. The inner end of this tube opens almost to the bottom of the cup.

   This end is closed, but on the sides are drilled 7 holes of 0.032 inch (0.8 mm) at irregular intervals to serve as air inlet holes.



   This arrangement determines a marked turbulence of the powder and thus ensures the complete emptying of the cup. The powder outlet tube is arched from the top of the cup to the top of the glass sprinkler tower.



   When the powder sample has been introduced into the tower, it is allowed to stand for 2 minutes before removing the foliage or treated insects. At each test, a square metal plate is placed in the tower and by weighing the amount of powder deposited on this plate, the amount applied per acre is calculated.



   Due to day-to-day variations in the results obtained by this test method, comparisons between the individual ingredients and their combinations were made simultaneously to reduce this source of variation.



   Slight modifications of this test used for par- ticular species of insects are as follows s
Epilachna varivestis - In tests with this insect, the foliage of jia-infested beans is sprinkled with Epilachna larvae after the third molt. These are left to feed for 24 hours, then the treated foliage is replaced by untreated foliage. Mortality is counted after 48 hours.



   Tetranychus bimaculatus - In tests with these insects, spiders are retained on the upper surfaces of pea bean plants by a "Tanglefoot" ring. The bean plants are placed in the glass tower and the spiders are sprinkled directly. Mortality is counted after 24 hours. Only adult spiders are used to determine mortality.



   Macrosiphum pisi - Pea plants are infected with these insects

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 and they are subjected to direct dusting. Mortality is assessed after 24 hours.



     Murgantia histrionica - The foliage is sprayed, then infected with insects. Mortality is assessed after 24 hours.



   Anasa tristis - For this test, pumpkin leaves are collected from the fields and the cut end of the petiole is wrapped in moist cotton wool. The individual sheets are then placed in 3.5 inch (9 cm) Petri dishes and sprinkled as described above. Each treated leaf is infected with 10 Anasa nymphs after the ninth moult, then the lids of the Petri vessels are replaced. After 24 hours, the treated leaves are removed and fresh leaves are introduced into the vases. The death count is done after the insects have been on untreated leaves for 24 hours.



    TURNTABLE PROCESS.-
House flies - This process is described in the article by Campbell and Sullivan, Soap and Sanitary Chemicals, 14 (6); 119-125,149 (1938). The tests are performed with slight modifications from the method described in this reference.



   The board used is equipped with 8 towers. The period between spraying and exposure of the flies to the settling fog is 6 seconds and the flies are exposed to the fog for 10 minutes.



  The sprayer works under 5 pounds / square inch (0.35 kg / cm2). 5 cc of the test solution is used for each test. Filter paper is placed at the bottom of each vessel containing the flies tested. Mortality is counted after 24 hours.



   The flies used in these tests were bred according to the standard procedures established by the Chemical Specialties Manufactures Association, described in the article "Peet-Grady Method" in the SOAP BLUE BOOK of 1952. The flies tested were 3 years old. days.



   The invention will be clearly understood by referring to the examples which follow, which cannot however limit it. The amounts are expressed therein in parts by weight unless otherwise indicated.



  EXAMPLE 1.-
All of the novel carbamates described are prepared by one of the following three synthetic methods: (A) reacting the appropriate isocyanate or the appropriate substituted isocyanate with the hydroxy compound; (B) reacting the appropriate chloroformate or substituted chloroformate with the amino derivative; (C) reacting the appropriate dialkylthiocarbamyl chloride with a suspension of an alkali metal salt of a hydroxyl compound.



   Thiol - and thionocarbamates are prepared similarly to (A) by reacting the appropriate isocyanate with a meroaptosubstituted compound or by reacting an isothiocyanate with a hydroxyl compound. Dithiooarbamates are prepared analogously by reacting isothiocyanates with mercapto-substituted compounds (analogous to (A)) or by reacting dialkylthiocarbamyl chloride with an alkali metal mercaptide (similar to (C)). These synthetic methods are described in more detail below. In Table 1, which follows, the names, melting points or boiling points and compositions of compounds which have not yet been described in the chemical literature are given.

   The synthetic methods of these compounds are considered to constitute evidence of their structures; analyzes are reproduced to indicate the degree of purity of the products.

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     Method A. - To a 1 mole solution of the appropriate isocyanate in 500 to 800 cm3 of anhydrous benzene containing 1 to 2 cm3 of triethylamine as a catalyst is added 1 mole of the required hydroxyl compound.



   The rate of addition of the hydroxyl compound is adjusted as needed to moderate the reaction. At the end of the addition, the reaction mixture is heated until the solvent goes to reflux, then is heated at this temperature for 3 hours. At the end of this period, the benzene is removed by distillation and its last traces are removed by distillation under reduced pressure. In cases where the product is a liquid, it is isolated by further distillation under reduced pressure. In cases where the product is a solid, the recrystallization is isolated and purified from aqueous ethanol or benzene / hexane solvent mixtures.



   Method B. - 1 mole of the appropriate amino compound dissolved in 400 to 600 cm3 of benzene is added to a solution of 1.10 moles of sodium hydroxide in 400 to 600 cm3 of water and the resulting mixture is stirred vigorously by adding the required chloroformate (1.1 moles) dropwise. The temperature is normally maintained at 40-50 C during this phase. When the addition of the chloroformate is complete, the reaction mixture is stirred at 40-50 C for 3-4 hours. The organic layer is then removed and washed with small portions of cold water until the washings are neutral. Benzene is removed from the washed solution by distillation and the latter traces are removed by distillation under reduced pressure.

   In cases where the product is a liquid, it is isolated by further distillation under reduced pressure. In cases where the product is a solid, it is isolated and purified by recrystallization of aqueous ethanol or of solvent-benzene / hexane mixtures.



   Method C. - To a stirred suspension of the required alkali metal phenoxide or marcaptide (1 mole) in 1500 cm3 of anhydrous toluene, the appropriate dialkylcarbamyl chloride is added in portions at a rate suitable for maintaining the temperature of the mixture. reaction at 40-50 ° C. When the addition is complete, the temperature of the reaction mixture is increased with continued stirring until the toluene is refluxed. This temperature is maintained for 6 hours. The reaction mixture is then cooled and the precipitated sodium chloride removed by filtration. The tolu- ene is removed by distillation and its last traces are removed by distillation under reduced pressure. In cases where the product is a liquid, it is isolated by further distillation under reduced pressure.

   If the product is a solid, it is isolated and purified by recrystallization of aqueous ethanol or benzene / hexane solvent mixtures.

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    TABLE I
 EMI10.1
 
 <tb> Carbamate <SEP> Process <SEP> of <SEP> Point <SEP> of <SEP> Point Ebul <SEP> <SEP> Analysis
 <tb>
 
 EMI10.2
 .9: 1: a tiQg fusion C lition Oc Thf, Q.riQ Tr.ouv
 EMI10.3
 
 <tb> Phenyl <SEP> N-Ethylcarbamate <SEP> A <SEP> 45-47- <SEP> N-8.48 <SEP> N- <SEP> 8.29
 <tb> Phenyl <SEP> N-Butylcarbamate <SEP> B- <SEP> 120-122 / 0.5 <SEP> mm.

    <SEP> N-7.25 <SEP> N- <SEP> 7.20
 <tb> Phenyl <SEP> N-tert.-butylcarbamate <SEP> B <SEP> 90-92 <SEP> - <SEP> N-7.25 <SEP> N- <SEP> 7.12
 <tb>
 
 EMI10.4
 Phenyl '-Dodgeylcarbamate B 54, 5-56, 5 - 1-459 N- 4, 59 Phenyl V-Furfurvlcarbamate B 83-85 - N-6.45 N- 6.38 Phenyï N- (2-Chlorophny1) -
 EMI10.5
 
 <tb> carbamate <SEP> ' <SEP> A <SEP> 55- <SEP> 56.5 <SEP> - <SEP> N-5.66 <SEP> N- <SEP> 5.70
 <tb> 3-Chlorophenyl <SEP> N-Isopropylcarbamate <SEP> B <SEP> 108.5-109.5 <SEP> - <SEP> N-6.56 <SEP> N- <SEP> 6.43 <SEP>
 <tb> 2-Chlorophenyl <SEP> N-Ethylcarbamate <SEP> A <SEP> 54.5-55.5 <SEP> - <SEP> N-7.02 <SEP> N- <SEP> 7.01 <SEP>
 <tb>
 
 EMI10.6
 4-Chlorophenyl i - Ethylcarbamate A 135-137 - N -7, 02 N- 7.04 4 4etl.zylphcnyl N-Ethylcarbamate A 108-108.5 - N-7.82 N- 773 4-Nitrophênyl N-Ethylcarbamate A 116-118 - N-13> 33 N-13,26 Isopropyl N-Cyclohexy1carbamate B 66-67 - N- 7,

  56 N- 7.59
 EMI10.7
 
 <tb> Ethyl <SEP> N-Furfurylcarbamate <SEP> B- <SEP> 78-79 / 0.5 <SEP> mm. <SEP> N- <SEP> 8.28 <SEP> N- <SEP> 8.09
 <tb>
 
 EMI10.8
 Ethyl N-tert.-Octylcarbamate B - 55-56 / 0.5 mm. N- 6.96 N- 6.90
 EMI10.9
 
 <tb> 2-Naphthyl <SEP> N-Ethylcarbamate <SEP> A <SEP> 128-129 <SEP> - <SEP> N- <SEP> 6.51 <SEP> N- <SEP> 6.33
 <tb>
 

  <Desc / Clms Page number 11>

   TABLEUA I (continued)
 EMI11.1
 
 <tb> Carbamate <SEP> Process <SEP> of <SEP> Point <SEP> of <SEP> Point Ebul <SEP> <SEP> Analysis
 <tb> preparation <SEP> fusion <SEP> C <SEP> @ ion¯¯ <SEP> Theory <SEP> Found <SEP>
 <tb>
 
 EMI11.2
 Furfuryl N-EthZTlcarbamate A - 91-92 / 0.5 mm. rt¯g2g Fi-8,17 5 - Chlor.oohenyl N, N-dimethyl-
 EMI11.3
 
 <tb> carbamate <SEP> B <SEP> - <SEP> 108-9.1 <SEP> mm. <SEP> N-7.02 <SEP> N-6.64.
 <tb>



  4-Chlorophenyl <SEP> N, N-dimethyl- <SEP> 6.79
 <tb> carbamate <SEP> B <SEP> 33.3-34.8 <SEP> 120-122 / 1 <SEP> mm. <SEP> N-7.02 <SEP> N-7.11
 <tb> Isopropyl <SEP> N-Methyl-N-phenyl-
 <tb>
 
 EMI11.4
 carbamate B - 110-112 / 10 mm. N -7.25 p1-, 2g Isopropyl N-Methyl-N- (3chlorophenyl) -carbamate B - 106-108 / 1 mm. m-6.15 N-6.27 Allyl N-Methyl-N. (3-chlorophenyl) -
 EMI11.5
 
 <tb> carbamate <SEP> B <SEP> - <SEP> 114-115 / 1 <SEP> mm. <SEP> N-6.21 <SEP> N-6.51
 <tb> Phenyl <SEP> N- (2-Hydroxyethyl) -carbamate <SEP> B <SEP> 87.0-88.0 <SEP> N-7.73 <SEP> N-7.69
 <tb>
 
 EMI11.6
 Phenyl N-Carbet7-, ioxymethylcarbanate B - 134-135 / 0.5mm. N-e, 28 Te-6., 27 Phn; r1 N- (3 nethoxypropyl) -carbamate B - 140-145 / 0.5 mm.

   N-6.70 'N-6.86
 EMI11.7
 
 <tb> Phenyl <SEP> N-Allylcarbamate <SEP> B- <SEP> 104-105 / 0.5 <SEP> mm. <SEP> N-7.91 <SEP> N-7.78
 <tb> Phenyl <SEP> N-Cyclohexylcarbamate <SEP> B <SEP> 136.0-137.0 <SEP> - <SEP> N-6.42 <SEP> N-6.42
 <tb> Phenyl <SEP> N-Benzylcarbamate <SEP> B <SEP> 82.0- <SEP> 83.0 <SEP> - <SEP> N-6.16 <SEP> N-6.07
 <tb> PhenylN- (2-Naphthyl) -carbamate <SEP> A <SEP> 169.0-170.0 <SEP> - <SEP> N-5.32 <SEP> N-5.41
 <tb>
 

  <Desc / Clms Page number 12>

 
 EMI12.1
 TABLE I 1 & tl
 EMI12.2
 Carbamate Boiling Point Method - Resaration Analysis fy.siQ! L De lii9n¯..Q¯- ThPari P! R0122 'Pt, P11Yl - (4¯gydroxTphenyl) -carbamate B .54.0-.55 , 0 - 1? - 6.1I¯ N-6.PO -3-tethylphnyl N-Ethylcarbamate. A 420¯44.0 - Dl -?, 82 fil -7; % 4 .LPljAnylph8ny1 N-EthylcarbAmate A 90.0-97.0 - 1'1-5.81 1-5.7 'Rpnzy1 N-Furfurylcarbamate B - 135-156 / 05 mm.

   T? -6, O6 1-6.9 1: -! Ithyl.urnbel.:1¯:ifrnzrJ. N-Ethylcarbamates A 1.7.0-198, 5 - N-5.67 rt-5, 5? Cyclohexsr¯ N-thy1carba1TIate A - '¯, 5-'2, 5 / t, 5 mm. F -A,? 5 1I-8,41 nphrmr1 'N - ". Ornho1inv1 cR: r> bama te" (N-Csrnopl1MI1rnrymor1JhoU.'oe) 1.0'7-1 () 8/0, n TT! 1 "" \. J \ 1-B, 76 z-6 75 (N - Car'hontor, ymorrhol.3¯nP) B 1, fi7 -1 n o, / n, lqm, fii -6,? 6 e75 nP110ny1 Fl-Pjrrroī1, di, nyTlca; bamate "(N-CRrbophenox.ypyrrolic1i" 1) B 7 4; o -7 5, o - N-7, 33 '-7,:' -; 9 Phny1 N-Ethy1t ': Üo1carbarnate A 82.5-85.5 - N-7.73 pi-7,?, .- n2nthtr: LPh'rrzTl carbâma Tl1-Ethy1 thj.o1- 5-93, rl¯ Bzz, carbamate A 91.5-93.5 yi -7, 17 xi -7, s? P h 4nyi N, N-Di Áthy1 thionocarbamate C 6.0-37.0 - N-6.69 N-6.05

  <Desc / Clms Page number 13>

 
 EMI13.1
 Jli. ' fl, t .4¯ .:

   11.-
Tests were carried out by the turntable method on house flies as described above using the indicated combinations of unsubstituted carbmas and phosphorus-containing compounds as indicated in Table 2. Tests carried out by the method of round on Tetranychus bimaculatus are described in Table 3.



   The results of these tests show that the carbamate combinations with the various organic phosphorus compounds have a well-defined synergistic activity.

  <Desc / Clms Page number 14>

 
 EMI14.1
 



  T. TABLE 2
 EMI14.2
 
 EMI14.3
 Carbamate Phoq-Qh2tg¯¯ ro.tai -6 ---; ---- Conëentrat1ëm-- ------- ë nëënt1'atoo Method - t in R ± gg jl.00 cm3L- Nom .ÜngL]. OO .- ± 11! ¯- d5EQujel test 24¯ hours ± 1¯ Propyl 500 - - Turntable ilusea domestica 1 - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - B-21/199 50 Turntable! 1ant Musca dompstïca 46 Propyl ' Q50 B-21/199 50 Turntable Musca do-nestica 62., ¯¯¯ .... ¯ .., ¯¯¯.¯..¯¯ .... ¯¯¯.,. ¯.¯ ..... ..¯.¯¯..¯ ..... ¯ .. ---.-...-- ¯¯¯¯¯ ----- .. ¯¯¯ ----------------- - C-4124 20 Turntable] \ [usca dome "3tica 46 Propyl, 100 C-4124 20 Turntable Musca domestica. 56 ---- ------------- ¯ .--------------- -------------------- -------- - - Diazinon 25 Turntable Musca domestica 23 Propyl 125 Diazinon 25 Turntable Musca domestica 35 =. ==: == -: = - == -:

  ======= - .. :: === ::: = -: =: .. - - - = ---- - - - = -p- - - ==: ==== - ..- - --- --..--- === - = ----- -Phenyl 500 - Turntable 1, Musca domestica 3 - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - Diazinon 20. Turntable Musca domestica 28 Phenyl 100 Diazin'on 20 Turntable Musca domestica 50

  <Desc / Clms Page number 15>

   T A B L E A U 3
 EMI15.1
 Carbamate H) NCOOR6 ¯¯¯¯¯¯¯ Phosnhata Cone. Conc. Clua1 '"1ti tR a Powder Powder (pounds / ït2fioP' Essa3¯ Fworta] 1 t R ¯.ili1.¯.¯- Nom¯ ¯01- act) ¯ ¯ hlfbodr d 'Egpa? ¯ S'11g! -1.



  Phnyl 0, 5 - - P9, 2 Tour Tetranynhus bi ^ acu1 atas 1 Malathion 0, 2.5 S'B, 7 Tour Tetrcmyc1îl1S bi1'1aculatus 66 Ph "I1.yl 0.5 Malathion 0.25 26.7 Tour Tpt1'anychus r-t '"' lacu18tus 98 -------------- F ---- ¯.-... 1¯ ----------- -----------------

  <Desc / Clms Page number 16>

 EXAMPLE III.-
A large number of phenyl esters of N-monosubstituted arbamic acids are tested in combinations with various phosphorus-containing acid derivatives having insecticidal activity. Tests carried out by the turntable method on house flies are described in Table 4. Tests carried out by the tower method on various crop insects and spiders are described in Table 5.



   In both series of tests, these combinations show a high degree of synergistic action.

  <Desc / Clms Page number 17>

 
 EMI17.1
 



  TABLE 4 R F NCOO --0
 EMI17.2
 Carbamate Phosphate 4 Concentration Concentration iI, iforta1i tp fI -'-) R ¯ ¯ m 100 cm 'Name JJglOO¯cm3) ¯ Method çl Test Suet¯ 4 heres R ¯ ¯ jga00¯cm L Xom¯ 24 heli-es Methyl 205 - - - Turntable tsusca 40mestica 2 - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - Malathion 100 Turntable {l1SCê omestica 2 Uét'r1yl 180 Malathion 36 Turntable u, ca (10- <, stîcn? 9 - Methyl Parathion 15 Turntable iTusca à # ne.tica? 3 Methyl 75 M: éthy1 Parathion 15 Turntable 1! fusca domeptica 54 Dodgcyl 500 - - Turntable - n01 '! Pc;

  t1.cC '12 - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - B-21/199 50 Turntable Musca clomestica 52 Dodécyl 250 B-21/199 50 Turntable Musca domestica 61 - - C-4124 20 Turntable Musca domestica 54 Dodgcyl 100 C-4124 20 Turntable Musca domestica 64 - - Diazinon bzz 25 Turntable Musca dorneptica 38 Dodécyl 125 Diazinon 25 Turntable Musca domestica 46 - Methyl Parathion.

   15 Turntable Musca domestica54 "Dodecyl 75 Methyl Parathion 15 Turntable Musca domestica 77 ¯-¯¯¯¯¯ --------------------------- ------------------------ -

  <Desc / Clms Page number 18>

   TABLE 4 (continued)
 EMI18.1
 tcarbam ate ¯¯ ----! PhQ ±] 2haE¯- Concentration Concextra, t.an mortality in R4 3 'N¯ōm (mg / 10Q - .. ± !!! 3) - "rIPthgde dEssai @et 24 hours m FurfU'ryl 500 - - Turntable Musea domestica 4 - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - -
 EMI18.2
 
 <tb> - <SEP> C-4124 <SEP> 20 <SEP> Plateau <SEP> turning <SEP> Musca <SEP> domestica <SEP> 54
 <tb> Furfuryl <SEP> 100 <SEP> C-4124 <SEP> 20 <SEP> Plateau <SEP> turning <SEP> Musca <SEP> domestica <SEP> 84
 <tb>
 
 EMI18.3
 -------------------------------------------------- .,

  ...--------- -
 EMI18.4
 
 <tb> - <SEP> Methyl <SEP> Parathion <SEP> 15 <SEP> Plateau <SEP> turning <SEP> Musea <SEP> domestica <SEP> 54
 <tb> Furfuryl <SEP> 75 <SEP> Methyl <SEP> Parathion <SEP> 15 <SEP> Plateau <SEP> turning <SEP> Musca <SEP> domestica <SEP> 74
 <tb> Isopropyl <SEP> 500-- <SEP> - <SEP> Plateau <SEP> turning <SEP> Musca <SEP> domestica <SEP> 10
 <tb>
 
 EMI18.5
 - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - -. ¯¯ - - C-4124 20 Turntable 1I1uf;

  ca èOT'1f'tiea. 68 1., <. = aizid, yTî. 100 C-4124 20 Domestica turntable 87 ¯¯-¯-¯ --- ¯ ---- L -------.------------------ ------------------------------------------
 EMI18.6
 
 <tb> ---- <SEP> Diazinon <SEP> 25 <SEP> Plateau <SEP> turn <SEP> Musca <SEP> domestica <SEP> 46
 <tb> Isopropyl <SEP> 125 <SEP> Diazinon <SEP> 25 <SEP> Plateau <SEP> tournarit <SEP> Musca <SEP> domestica <SEP> 68
 <tb>
 
 EMI18.7
 --------------------------------------------- ----- --n- $ ut. 500 - Plate, at the turn lIfusea domest4ca. 6 - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - Diazinon 25 Platea.u turning Musea domestica 26 n..Buty1 125 D3.ain3n 25 Turntable liru sea domestica 44 --------..... ..-------------------------- ----.-.gold-------------- -...

   - "'-
 EMI18.8
 
 <tb> Methyl <SEP> Parathion <SEP> 15 <SEP> Plateau <SEP> turning <SEP> Musca <SEP> domestica <SEP> 58
 <tb> n-Butyl <SEP>. <SEP> 75 <SEP> Methyl <SEP> Parathion <SEP> 15 <SEP> Plateau <SEP> turning <SEP> Musca <SEP> domestica <SEP> 83
 <tb>
 
 EMI18.9
 ¯ ...... ¯¯ ... ¯ ¯¯., .. ¯.¯¯ .......... ¯C ^ 124 --¯ --. --- .-- 2Q ---- P1ateflü- toiîrnant --- füSëa- domestica, 55 n-Butyl 100 C-4124 20 Turntable 1I: 1: usca domestica 67 - ¯ ... r ..... r ¯ J ¯ .. ¯. - ... ¯ .. ¯w -,.,. .r - ¯¯ .-- w ----- ¯ ------,, ¯-, .. ¯ ... ----. --- ..------- --- .. ¯.,. Rr.r --........ r, ... ¯.¯..a., 4 -------

  <Desc / Clms Page number 19>

 
 EMI19.1
 TABLE 4 (gnite)
 EMI19.2
 Carbamate ----- 'Phosphate Concentra t Name Coneentraton Test Method Subject P4 clash, in im.gLlO {Lfm! ¯¯-':

  "No !!! ¯- img / lOÇL2n! ¯.l- Mpthod.ê-d 'Es ±! Subject? 4- hours ± <) ¯ Tert. -Butyl 500 - - Turntable jjusea domestica. 4 - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - B-21/199 50 Turntable Musca domestica 65 tert. -Butyl 250 B-2lfl99 50 Turntable usca dome sti ca 74 -.

   C-4124 20 Plateau tourna. "T l1ca cl'1MPti" c 64 tert. -Butyl 100 C-4124 20 Turntable 7Tusca 0ornE'stiea 82 - - Diazinon -¯ 5 Turntable 11J.sca domostier. 4 z¯¯¯ ut; l 1? 5 Diazinon 25 Ptatqat t01JT> T'lfI'Y "t H" ca 00moti, .. 57 Allyl Ilioo dom; stica 1 - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - Di a zi no 20 Turntable u.sca co! estica- 98 Allyl 100 Diazinon 2,0 Turntable r1Tnca c10T'Ir? tic. 64 = --------- == ------- B-21! 199 ---- 40 Turntable lilusea doresttep 40 Allyl 200 B-21/199 4E Turntable Musea domestica 70 - Methyl Parathion 10 Turntable Musca domestica r 38 Allyl 50 1lethyl Parathion 10 Turntable Musea domestica 72 500 ¯¯ '- - - ¯ Turntable Musca ¯.

   dômestica - - ¯ -4 2-Hydroxyethyl -500 - Turntable Musea domesti # ------- - - Methv1 Parathion 10 Turntable Musea domestica - 33 2-Hydroxyethyl 50 Methyl Parathion 10 Turntable Musea domestica 42 - - C-4124 15 Turntable liuseâ dorestica 54 -rydroxyethyl 75 C-4124 15 ¯ ¯ Turntable 1! Usca domestica 61

  <Desc / Clms Page number 20>

   TABLE 4 (continued)
 EMI20.1
 
 <tb> Carbamate <SEP> Phosphate <SEP> ortalitg
 <tb> .concentration <SEP>, Concentration <SEP> Mortality
 <tb>
 
 EMI20.2
 R (M-gLlQo - CM-31- Q !! L imgL100 ± !!! 1! ÉthQ.9; e d'ê. !!!., Ê.uje.: T mlh.glE.Ún.



  - B-21/199 40 Turntable nusca domestica 53 ... Hyd, roxythyl 200 B-21ll99 40 Turntable Musca domestica 78 --------------------- ----- .. p ---------- --------------- d.-P4ethogy7. -500 - - Musca domestica 2 turntable
 EMI20.3
 
 <tb>
 <tb> - <SEP> Methyl <SEP> Parathion <SEP> 15 <SEP> Plateau <SEP> turning <SEP> Musca <SEP> domestica <SEP> 90
 <tb> 3-Methoxypropyl <SEP> 75 ' <SEP> Methyl <SEP> Parathion <SEP> 15 <SEP> Plateau <SEP> turning <SEP> Musca <SEP> domestica <SEP> 100
 <tb>
 
 EMI20.4
 - B-21 / l99 50 Turntable lfusca domestica 84
 EMI20.5
 
 <tb> 3-Methoxypropyl <SEP> 250 <SEP> B-21/199 <SEP> 50 <SEP> Plateau <SEP> turning <SEP> Musca <SEP> domestica <SEP> 91
 <tb> - <SEP> Diazinon <SEP> 25 <SEP> bzz ^ <SEP> Plateau <SEP> turning <SEP> Musca <SEP> domestica <SEP> 62
 <tb>
 
 EMI20.6
 3-Methoxypropy1 125 Dia. 2,

  inon 25 Domestica turntable 78 ë # cl hex # l 500 Musê-a-domë'Stica turntable 6 - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - -
 EMI20.7
 
 <tb> - <SEP> - <SEP> B-21/199 <SEP> 40 <SEP> Plateau <SEP> turning <SEP> Musca <SEP> domestica <SEP> 30
 <tb> Cyclohexyl <SEP> 200 <SEP> B-21/199 <SEP> 40 <SEP> Plateau <SEP> turning <SEP> Musca <SEP> domestica <SEP> 42
 <tb>
 
 EMI20.8
 Diazinon 20 Turntable Ilusea domestica 19 Cyclohexyl 100 Diazinon 20 Turntable Musca domestica 38 Benzyl 500 - Turntable Fiusca domestica 8 - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - Methyl Parathion 10 Turntable Musca domestic91 22 Benzyl 50 Igethyl Parathion 10 Turntable 7.usea domesti6,

  at 40
 EMI20.9
 
 <tb> C-4124 <SEP> 15 <SEP> Plateau <SEP> turning <SEP> Musca <SEP> domestica <SEP> 44
 <tb> Benzyl <SEP> 75 <SEP> C-4124 <SEP> 15 <SEP> Plateau <SEP> turning <SEP> Musca <SEP> domestica <SEP> 62
 <tb>
 

  <Desc / Clms Page number 21>

   TABLE 4 (Continued)
 EMI21.1
 Carbamate Phosphate R4 -Concentration -Concentration Mortality- in R (m 100 ç Nom.! Mg! 100 cm, Ptest method Subject 24 hours lÎ 'B-21/199 40 Turntable Musea doaestica 26 BenZ "1 200 B- 21/199 40 ¯ Turntable 1,

  fusca domestiaa 52 4-Chloroghnyl- ¯ ¯ 500 - ¯ - - Turntable 1! usca domestica - Methyl Parathion 10 Turntable Musca domestica ¯ ¯ 22 4-Chlorophenyl 50 1 ± Methyl Parathion 10 Turntable lfusea domestica 34 B- 21 199 ---- 40 BÙ% ôûin # 'â7à @@ 26 4'Chlorophgnyl 200 B-21/199 4Ô Turntable' 4usca domestica 58 - --4.- ---- 4-HydrqxyphénYl 500 - Plateau turning Musea damestica 2 1 \ "- - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - Methyl Parathion 10 Turntable Musca domestica 24 4-Hydroxyphenyl 50 l4lethyl Parathion 10 Turntable Musea domestica 48 I-Naphtyl- ..

   -500 - ---- - TurntableMusea domestica '2 C-4124 15 Turntable rlusea domestiea r! ¯ 40 1-Naphthyl 75 C-Qi24 15 Turntable Musea domestica 54 IT B-21 199 40 Turntable Musea domestica 40 1-N aphthyl 200 B-21/199 40 Turntable Musea domestica 57 z-nanhthyl 500 4 - - Musca domestica turntable 1 - - - - - - - - - - - 15 Musks turntable. domestica 55 2-Naphthyl 75 C-4124 15 Turntable Ilusea domestica 66 - - Diazinon 20 Turntable Uusca domestica 48 2-NaphthYl 100 Diazinon 2f) Turntable Musca domestica 70 - - <q7 \ .. J-t

  <Desc / Clms Page number 22>

   BOARD
 EMI22.1
 
 EMI22.2
 
 <tb> Carbamate <SEP> Phosphatē¯¯
 <tb> Conc. <SEP> Conc. <SEP> Quantity
 <tb>
 
 EMI22.3
 Powder Name Powder (lbs / hqq! Q of Test Only- Mortality.

   11L¯- Name 00-- acre, q4lL ¯ - ± jJ! - (i ± ¯¯¯
 EMI22.4
 
 <tb> Methyl <SEP> 1 <SEP> - <SEP> - <SEP> 9.4 <SEP> Tour <SEP> Epilachna <SEP> varivestis <SEP> 0
 <tb> - <SEP> - <SEP> Parathion <SEP> 0.25 <SEP> 4.0 <SEP> Tour <SEP> Epilachna <SEP> varivestis <SEP> 22
 <tb> Methyl <SEP> 1 <SEP> Parathion <SEP> 0.25 <SEP> 3.8 <SEP> Tour <SEP> Epilachna <SEP> varivesti <SEP> s <SEP> 100
 <tb> Methyl <SEP> 1 <SEP> - <SEP> - <SEP> 16.0 <SEP> Tour <SEP> Tetranychus <SEP> bimaculatus <SEP> 2
 <tb> --- <SEP>. <SEP> Malathion <SEP> 0.25 <SEP> 16.0 <SEP> Tour <SEP> Tetranychus <SEP> bimaculatus <SEP> 39
 <tb> Methyl <SEP> 1 <SEP>, <SEP> Malathion <SEP> 0.25 <SEP> 17.2 <SEP> Tour <SEP> Tetranychus <SEP> bimnculatus <SEP> 94
 <tb> Methyl <SEP> 1.

    <SEP> - <SEP> - <SEP> 20.6 <SEP> Tour <SEP> Murgantia <SEP> histrionica <SEP> 10
 <tb> - <SEP> - <SEP> Malathion <SEP> 0.5 <SEP> 20.6 <SEP> Tour <SEP> Murgantia <SEP> histrionica <SEP> 30
 <tb> Methyl <SEP> 1 <SEP> Malathion <SEP>. <SEP> 0, <SEP> 5 <SEP> 17, <SEP> 2 <SEP> Tour <SEP> Murgantia <SEP> histrionica <SEP> 90
 <tb> Methyl <SEP> 1-- <SEP> --- <SEP> 10.0 <SEP> Tour <SEP> Epilachna <SEP> varivestis <SEP> 1
 <tb> Malathion <SEP> 0.5 <SEP> 10.0 <SEP> Tour <SEP> Epilachna <SEP> varivestis
 <tb> Methyl <SEP> 1 <SEP> Malathion <SEP> 0, <SEP> 5 <SEP> 10.0 <SEP> Tour <SEP> Epilachna <SEP> varivestis <SEP> 90
 <tb> Methyl <SEP> 1 <SEP> - <SEP> - <SEP> 15.0 <SEP> Tour <SEP> Epilachna <SEP> varivestis <SEP> 8
 <tb> --- <SEP> Diazinon <SEP> 0.25 <SEP> 15.0 <SEP> Tour <SEP> Epilachna <SEP> varivestis <SEP> 15
 <tb> Methyl <SEP> 1 <SEP> Diazinon <SEP> 0.25 <SEP> 15,

  0 <SEP> Tour <SEP> Epilachna <SEP> varivestis <SEP> 73
 <tb>
 
 EMI22.5
 1¯¯¯, ¯¯¯¯¯ -----, - l ------------------------------- -------------.--.



  Éthßl 1 - - 19.6 '¯ Tower Epilachna varvéstis - ""' - "'-" ¯
 EMI22.6
 
 <tb> - <SEP> Malathion <SEP> 0.5 <SEP> 19.1 <SEP> Tour <SEP> Epilachna <SEP> varivestis <SEP> 77
 <tb> Ethyl <SEP> 1 <SEP> Malathion <SEP> 0.5 <SEP> 12.5 <SEP> Tour <SEP> Epilachna <SEP> varivestis <SEP> 100
 <tb> Ethyl <SEP> 1 <SEP> - <SEP> - <SEP> 8.3 <SEP> Tour <SEP> Tetranychus <SEP> bimaculatus <SEP> 5
 <tb> - <SEP> - <SEP> Malathion <SEP> 0.5 <SEP> 4.8 <SEP> Tour <SEP> Tetranychus <SEP> bimaculatus <SEP> 44
 <tb> Ethyl <SEP> 1 <SEP> Malathion <SEP> 0.5 <SEP> 4.3 <SEP> Tour <SEP> Tetranychus <SEP> bimaculatus <SEP> 100
 <tb>
 

  <Desc / Clms Page number 23>

 
 EMI23.1
 VS --;

   t e P ho -P, i- te T! 3ZEAU 5 sLVī te, Conc. 'Conc. anttté 4 Powder Powder Cii vres /?; ro r ta.1i t ô àL¯ Name i! L¯- -2: 9rgL- r.éthQê-Q, -'- SUjJzi ¯.-11) ¯¯Ethyl 1 - - g8 Tour Hurgantia histrionica 0 - Malathion 0, 5 8, 8 Tour Murgantia h1striol1ica E. # 1 1 Malathion 0, 5 5.7 Tour 1.! iirgantie. hi strionica 70 Ethyl.

   1 - - ', 5 Tour Maerosiphum pisi Il - - Ilalathian 0, 5 8.8 Tour Maerosij} hum pisi 82 Ethyl 1 Valpthion 0, 5 6.4 Tour rflaerosiphum pisi 95 Ethvl 1 - - 24.9 Tour Epilachna varivestis - Diazinon 0.25 20.9 Tour Epilachna varivestis 35 Ethyl 1 Diazinon 0.25 1.7 Tour Epilaehna varivestis 58 Isopropyl 1 - 25.2 Tour RotlaebI1a vprtvestis 5 - - ïLw1'tnian 0, 5 20.3 Tour Epilachna varivesfiis 57 1 1 Ialat'nicn 0.5 20.1 Tour Epilaehl1a varivesti s zou 1 Isopropyl 1 - - 10.4 Tour Tetranychus birn ['cu1a tus 2 - - Malathion 0.5 8.0 Tour Tetranychus bi , -iiculat * us 59 Isopropy1 1 Malathion 0.5 8.0 Tour Tetranychus bi ::

  czla.tns 1¯00 n-'BntYl - 1 - 17, Tour Epilachna varivpstis - Malathion 0, 5 19, 8 Tour Er, ri1aehna. v2ri vst ?. s 5 n-Butr1 I. 1.1a1athion 0.5 14.0 Tour En3laehna varivestl.s 95 n-Butvl 1 - - 16.9 Tour Pdurgantia histrionica - - - Tialatnion 0, 5 19, 3 Tour Murgantia hi strionica 0 n-Butyl 1 Ma1athion 0, 5 Il, 2 Tower Murgantia histrionica 70 tert. -Butyl 1 - - 35.0 Tour Epilaehna varivestis 0 IT "'- ldalathion 0, 5 25, 9 Tour Ep11achna varivesti s 30 tert. --Butyl 1 1! Alathion 0, 5 33, 8 Toùr Epilachna varivesti s 100

  <Desc / Clms Page number 24>

 
 EMI24.1
 Carbarnate s¯Tyl-la TABLE 5. (Continued) Carbamate Phosphate "# Cone. Conc.

   Quantity Powder Powder (pounds / Fortalitë ± 1¯ --- Powder Name Powder (pounds / r2ethoid of Test Suj "t ¯ ± µ1¯¯¯¯ Dojccyl .1 M-1- thi xe -.9 Tower Tetranychu8 bimpcilatiir, Malathion 5; 5 18> 3 Tour Tetranrhu! 7, 1) µÎ $$, lÎÉ'l (1 Malathion 0.5 10.0 Tour Teotranychus n; Y! '. É' ("l] at'1s 22 1> c : dËicy1 1 Malathion 0, 5 11.2 Tour Ttrar.zrclus bJ.r1rc'il.atus 72 3-MSthoxy- propyl 1 - - 8.0 Tour Tpt'NI.'I1ych1.18 b: tJr.1cnln. tus 10 Malathion 0, 5 10, 7 Round Epilachna variVf'Jt1.s 0 S-M4thoxy- 1 Malathion 0, 5 10, 2 Round Epilachna var3 resfii. 80 propyl "phn, l 1 --- ¯- 96 Round Tetranychus bi - ,,, culatus 2 - - Malathion 0, 5 6.1 Tour Tetranychus bimpeul.atus 10 Phnny 1 Malathion 0, 5 9, 7 Tour TetrDf1Tcl1.us':

  i ^ .culatus 100 2-Chloro- phenyl 1 - - 7.5 Tour Tetranychus bi9 ('u1tus 7 - Ma.lathion 0, 5 7, 2 Tour Tetranychus bi' r ('u1atus 41 2-Chlàro- 1 Malathion 0, 5 4, 3 Tour Tetranychus biY'1tcu1atus 51 phenyi Furfllrv1 1 - - 9.4 Tour Eoilechna vn.rivestis 5 - Malathion 0, 5 Il, 3 Tour Enil.achna varivesti s 15 Furfuryl 1 Malathion 0, 5 11 , 0 Tour Epilachna varivestis 100 Furfuryl 1 - - Il, 5 Tour Macrosiphum pi si 9 - - Malathion 0, 5 9.7 Tour Macrosiphum pisi 82 Furfuryl 1 Malathion 0.5 102 Tour Macrosiphum pisi 100 Furfuryl 1 - - - 10, 7 Round Tetranychus bima c1Jlatus 2 - - Malathion 0.5 10, 7 Round Tetranychus bimaculatus 2Q Furfuryl 1 Malathion 0.5 6y7 Round Tetranyehus bimpculatus 100 Furfuryl 1 - - there, 0 Round Murgantia histrionica 0 Malathion 0, 5 17.6 Tower Murgantia histrionica 30

  <Desc / Clms Page number 25>

 
 EMI25.1
 Carbamate Phosuhate ---------- --- Cone.



  Powder Cone. Quantity Mortô1t 4 ill # - Name Powder (pounds /] ## --- # (%) ¯¯ ¯acrel¯ Métl1odd'Essgi Suj [e Fufuy1 1 Malathion 0.5 '19.2 Tour, Zurantïa hisirionica 10C' ethyl 0.5 - - 48 6 Tour Anasa tri sti s - Ma1athion 0, 25 48.6 Tour Anara tri s ti s 10 Methyl 0.5. Malathion 0, 25 46, 2 Tonr Anasa tri stis 100 EthY1 1, 0 - - 48, 8 To, x¯r Ar.a sa sad 0 - - f, lal: t1, :: t011 0, 25 46 ,? 'Tour Anaa trstj8 Fthyl 0, 5 T ala thion 0 , 25 46, l Tmlr An2-sa tri. Sti SO Isopropyl J, 0 MatnoT'T ########### T - Malathion 0.5 51.9 Tour A'1 :: a tr: # .st:

  is Isopropyl 1.0 '' fa1athio'l 0.5 46.0 Tour Anasa t¯ri stis 90! 3utYI 1.0 - - 8.1 Tnr Aw a sa t, .. isti.s 0 - Malathion n, 25 27.6 T ('t'lr Arasa tr1 st5 Eiit'YTl 1,0? <l al athi ov 0, 7.6 Tour Arasa tri 1 t 3¯ 1 I00 tert. -But yI 1.0 - - 28.4 Tour Anôsa tri.stls 0 - - i \ 1alathion 0.35 46j6 Tour Al1Ctsa tristis ter. t. -3utT1 1.0 Malathion 0, 5 26.8 Tour Anasa tri stis 80 3-! Jt'hox: r- 1.0 - - 31.6 Tour Anasa tristis0 "" pro 9yl - Malathion 0, 5 26, 5 Tour Anasa tri sti s 3 - :, ét110x; r- 1.0 Malathion 0.5 28.7 Tour Anasa tristis Q0 prooyl CārbonnPthVTl 0.5 - - 46.0 Tour Anasa tristis ##### ######## 0 "" - 'falatl1io11 0; 25 45.6 Tower Anasa tristis fl Ca roo: "' TH1 (lt1:

  l.yl 0.5 1-IalatM.on 0.25 47, S Tower Anasa eris ti s & 0

  <Desc / Clms Page number 26>

   TABLE 5 (continued)
 EMI26.1
 
 <tb> Carbamate <SEP> Phosphate
 <tb> Conc. <SEP> Cone. <SEP> Quantity
 <tb> Powder <SEP> Powder <SEP> (books / <SEP> Mortality
 <tb>
 
 EMI26.2
 5 --- = :. TIfL- Name - -5Q}: gL M: t.bQ {! ± .¯d'P; si. 81.110.1. (IL ## C.Yt.:lnl1rx;rl 0,5 - - bzz 2 Tour Tptranvchu.p 'hi! Ja11'.t ", f' - l1alf'thion 0, a5 10 7 Tour Tour Tetranvebus' hi "" [I ('11Jrtu fnc 9 Cycl.ob rµyl, 0, 5 a7¯athion 0, 25] ¯2) 0 Tour Tetranychus birnrctll1'1tns 70 A' 1, rl 0.5 - - 12.3 Tour Tetranrc111H1 1) imaC111 pt, "s 1 - - pMala.thi on 0, 25 13, 2 Tour Tetra%, r!? T1'ts b: iJ" "I" 1f ", 'l t1J [ :

   61 1 \ 11, "r1 n, 5 Malathiou 0, 25 12.0 Tour Tth3 'hi.' '' F1C''1.tus 10n A1ly1 0, 5 - - 51, 5 Tour Iri a sa tri 8t; . 0 ¯.¯ '- l \ 1alat'hton 0, 25 29.2 Tour.-41- asat ri, r t', "1.1.) 71 0, 5 Malathion 0. 25 27.0 Tour A, "[H1A a ri, s tī 100 Phnny1 1.0 - - 49, 4 Tour Anasa trintip - - Hlathiol1 0, 25 46, 6 Tour ànasa. Tristis 0 'hnrl. 1 ., 0 Malathion 0,2,5 47,4 Tour AnaA3 tristis 70 1-Í \ Japhthyl 0, 5 - 26; 5 Tour Tptt'anych1J ht "" '8C1ÜRtl.18 10 - - II, T'1.1athio ! l 0, P.5 2'4.3 Tour Ttranrchus' hi. "fY \ 8Cl,] rt1, 58:! .- nlanhth5T7. 'Q, 5 Malathion 0.25 21.4 Tour Tetranychu3 h: i.1 "I1! 1 cnlatt1 93 1-Naphthyl 0, 5 - - 52, 3 Tour JI'.AR tri sti.



  Is there tl-11? V1. 0.25 46.2 Tower Anasa tristis 0 J-Tl1anhthYl 0.5 Malathion 0.2.5 46.6 Tower Anasa r3 s tQ s 60
 EMI26.3
 
 <tb> Furfuryl <SEP> 0.5 <SEP> - <SEP> - <SEP> 42.7 <SEP> Tour <SEP> Anasa <SEP> tristis <SEP> 0
 <tb>
 
 EMI26.4
 - - Malathion 0, 25 46, 6 Tour Anasa tri sti s 10
 EMI26.5
 
 <tb> Furfuryl <SEP> 0.5 <SEP> Malathion <SEP> 0, <SEP> 25 <SEP> 44.4 <SEP> Tour <SEP> Anasa <SEP> tristis <SEP> 80
 <tb> Benzyl <SEP> 0.5 <SEP> - <SEP> - <SEP> 7.2 <SEP> Tour <SEP> Tetranychus <SEP> bimaculatus <SEP> 0
 <tb> - <SEP> - <SEP> Malathion <SEP> 0 ', 25 <SEP> 8.0 <SEP> Tour <SEP> Tetranychus <SEP> bimaculatus <SEP> 25
 <tb> 'Benzyl <SEP> 0.5 <SEP> Malathion <SEP> 0, <SEP> 25 <SEP> 5.3 <SEP> Tour <SEP> Tetranychus <SEP> bimaculatus <SEP> 100
 <tb>
 

  <Desc / Clms Page number 27>

 EXAMPLE IV.



   Another group of compounds comprising the substituted henyl esters of N-monosubstituted carbamic acids in combination with various derivatives of acids containing phosphorus and possessing insecticidal activity were tested for testing. The tests carried out by the turntable method on house flies are described in Table 6.



  Tests carried out by the tower method on various crop insects and spiders are described in Table 7.



   These combinations also exert a marked synergistic action.

  <Desc / Clms Page number 28>

 
 EMI28.1
 



  'p.T, s'. TT
 EMI28.2
 
 EMI28.3
 ¯¯¯¯¯ .C cl "r'h1.trn Rt." 'F ¯¯¯¯ ¯ ¯¯ Phosphate ¯¯.¯¯..¯ ....... ft nor ¯¯¯¯ .. ..¯..Cna. '1.00 r.m m. r'PtYio d'Fssai tyFt '1o-rt.; 111. +> --....... 5.¯ --- Coc. (/ 100 crr3) MÁthorl (1 d'Essai Rulet (".n 94. '!: <; 11r "'¯¯ ... ¯..¯¯¯¯ 100 0!" "" '' "" '' r.r-i-'T'7; p '. 0-ChlOY'onhf> nYl '"' 500 '" - - 1? 1 <'1tpP1' tnl1Y'i1r.'rt <11, ct4 rk \ yrpti.Cf.1 -. - - - - - - - - "- - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - --- - - B-33/199 50 Platpan t011TI "pnt Ml1; .1C (1. Dr = 1 - =% stj¯ca tO .t -:" 11T1T'T1VlJ. T, ¯C.:] Ol¯i, xnnrc ' l; j1 2 50 B-21/199 50 Turntable "\" '11C8 no!' \ 1 '' '' 'st .. ('? 84 - - - C-4-124 20 'P] ,;: tr81 'tOl.l'Y'Y] f-1.nt H'1r'1 (' / '1 "3 61 IA () 11' () n: rl; /.,-. r.hlnY 'ontl' -; Yl; tl j¯00 0¯1.!. 1? ti, -.

   Pl.d'i; r11 tOl1.T'Y18nt Tllf '(' (1 rl0rn "'sti.rt ryl - - -" - - Di.A?,;' Y \ (I! 1 1 'DF P1.At.rFll1 trmT'Y1FIY1t;, Tl1; .1CFl p (4, o. C 4 "(1,) f ', Il'VJ 0-ChJ nT'onh? N: vJ. 1? F nlc'1 ? '! Y (an z? 5 P1tÎlml turning "t71 t clomestica. 55 Mét'l1yl Parathion 15 P1at0.t: 11 tO'1Y'Y1nt Muscn 00mestica 55 ..t.sor) 1opy1?, ¯Go'1C> T 'r7;') 11t'p'.rJ- 75 'IthT = 1. Pr1-ài-hJ, oln 15 Turntable' Tl1ACé'1 domestica. 64 Ft} lyl 4-Ch1orophény1 500 - - Turntable liilqca c10ynnstica 1 - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - Methyl Parathion 15 Turntable Musca c? OIl! Cst3ca. 13R> t.-, 't..4-Chlaxophr1, T1 75 Methyl Parathion 15 Turntable Musca (10-m-rtica 80 sthyl 3-M6thy1phény1 500 - - Turntable Musca domestica 4 - Methyl Parathion 10 Plat0, lJ turning 1 \ iusca. Clomostica 19 Rtl1; rJ.

   S-M4thylphenyl 50 Methyl Parathion 10 Turntable usca domesti.ca 64

  <Desc / Clms Page number 29>

   TABLE 6 (continued)
 EMI29.1
 R -11 iCOOR6 Carbamate ln'-1? Carbamate H ## PoIIte g Conc. (Mg./ Co-c.ro-./ tho a.5 vj / ô 'À à i BL- lQO¯cm3) ¯¯¯ Il T¯00 1.00 cil Mthop¯ d / Test Su-'Ft-, Ethyl -li6thylphFnyl 500 - - F1¯at? z turning Musca dor; C = + ± ¯T / ---- ¯ ------------- ---------------------------------------------.



  - Mëthyl Perahion 10 Platean toīirlaz-mt '", 2 40--' = s + 1 oefl Ft'-1j, Tl, 4-Met'bvTuhpnyl 50> ± 4thirj¯ Parathion 1.0 v7.afatZ tOLtrnant ''. , ç rn, dopHtica? fi - # C-41 '? A 15 P7.atAa, 1 oat.' ii; gra <vmmr + <¯ca 70 Ethyl 4¯r.lPthjr7 nhnTl 75 C¯ [9d lu P? at e / i> j-ni.rrw,.,; -. j-? 1, sr8 dm --- psts¯ r> 5 ### '' "" #### Et't-iirl 5on µIatpLnu tn -ur - iant Ethyl 4-T.tonbyl 500 - Turntable-;., +> i ca éom-rrti, ca tl 10 t, 'l7rrp,. ,, .- ù>, so> FÀ <-o <1¯ra i? Ft''1 Tl 4-T'L'TOftl'tnVl 50 i,] Ft'Ji + 1 Pa.ra.thion 10 Plat-aii tournart - = ,, çr? aoi-r, utj = p to C-4134 15 PJ..1 - ', t tottYtant' ">, sPa rl nri - c + its Ethyl 4-? ijt, n;, hg. ,,, ri 75 C- el¯.124 j5 pia + =? ij + oi, r-; 1 iTi, çc, an --- mt <= a po

  <Desc / Clms Page number 30>

   TABLE 7
 EMI30.1
 Carbamate P R 4:; ::; lCOOR6 Carbamate ¯¯¯¯Phosphate onc. - Conc.

   Quantity Powder Powder (pounds / Method?, <mortality fl = R -1 Name Î acre) of Test Subject ¯ Ethyl 2-Chlorophenyl 1 - - 9.6 Tower Tetrarychrs bimaciila-tus 0 - Malathion 0.5 7.2 Tower Tetranychus bimaculatus 41 Ethyl 2-Chlorophenyl 1 Malathion 0, 5 6, 2 Tower Tetranychus bimaculatus 97.5 Isō ropT. 3-Chloi-uphenyl 1 - - 9.6 Tour E-nil -ckcb-na varivestis 0 - Malathion 0.5 lOe2 Tour Epilachna varivpstis 25 IBoJ1ro1Jr1 3-Chlorophenyl 1 Malathion 0.5 8.3 Tour Fpilachna varivestis 60 Isopropyl 3-Chlorophenyl 1 - - 36.6 Tour Murgantia histrionica 0 - Malathion 0.5 33.0 Tour Y-urfpantie.

   histrionica 30 Isopropyl 6-Chlorophenyl 1 Malathion 0.5 305 Tower MurgaTitia histrionica 90 Ethyl 4-Chlorophenyl 1 - - 80 Tower Tetranychus bimaciilptiis 5 - - Malathion 0, 5 6, 4 Tower Tetranychus bimaculatus 29 Ethyl '4-Chlorophenyl 1 Malathion 0, 5 7.0 Tour Tetranychus bimaculatus 100 Ethyl 4-Mêthylphenyl 1 - - 9.4 Tour Tetranychus b, macuZ.atus 1 - - Malathion 0, 5 9j3 Tour Tetranychus bimaculatus sa Ethyl 4-t, lethylphenyl 1 Malathion 0.5 z Tower Tetranychus bimaculatus 100 E1 4-iJitrophenyl 1 - 8.8 Tower Tetranychus bimaculatus 1 - - - Malathion 0, 5 9, 3 Tower Tetranychus bimaculatus 88 Ethyl 4-Kitrophênyl 1 Malathion Q, 5 z6 Tour Tetranychus bimaculatus 100 Isopropyl 6-Chlorophenyl 1.0 - - 32, 7 Tour Anasa trbti 0 - Malathion 0.25 2716 Tour Anasa tristi 0 Isopropyl 3-Chlorophenyl 1.0 Malathion 0.25 27,

  9 Tower Anasa tristi 100

  <Desc / Clms Page number 31>

   TABLEUA 7 (continued)
 EMI31.1
 4 R ---- Carbamate Phosphate Carbama% e Conc. 'Phosphate Conc. quantity Conc. Cone. quantity P4 Powder Noat Poudré (lIvre sI {otaH. + f L 4-Chloro hén !! 9l !! - !! ± L Héthoele d'Esso gu.fet Ù 'Ethvl 4-CblQrophénYl 1.0 50.8' l ' our An? qa tnstis Ethyl - J! alathion O 5 46,1 Tour A'I "\ a tristis Ethyl 4-Chlorophény1 1,0 Ua.lathion 0, 5 5!., 2 Tour A'1I '! tl" f sti s 100 Ethyl .3-me: Fipi 0,, 5 13.0 lalathion Ou5 Tour tr¯; cti Ethyl 3-M ethyJ.phenyl 0.5 - -.

   Il, 2 TNtI 'TRtra "", chns bilT'acula tus 0 Ethyl Z-Mé-thylph4,, iyi - ion 0.25 10.4 Totir Tetranvchus birnaculatus 15 BthyI 3-Methyl!> H4nYl 0, 5 Malathlor- 0 , 25 10.4 TB ,, ir 'rpt "' chus biacnlst" s 99 Ethyl Z, 5-Dinethylphenyl 0, ¯¯ 5 - - - 10.5 Toiir? Mrramebvs hiracul a tus 4 ct f .. {alatlon 0 , 25 6 rnlir '1' .... t "'V" ,, "'" hi "" :: \ c "ltn!" 66 -;, Ethyl 5-Dit- 'the hényi 0.5 4a! Athi-an 0.25 12'6 T ,, 7T t-ti-r! E! 5thyl 3,5-Dil !! pthYlphenyl 0, .5? .. {a1ath1n 0.25 '1 ,? 'l'n - ,, ..'! '' '' T '' '' I "\ :, r ('' ht + bim111tu 100 Etl1; rl. 4-] ethoxyphp.nYl 0.5 12, -e Tonr Tn '' '' '' '' '(' '"tl hÍ"'; lculh, s Ethyl 4-: i 'thoyyohényl Ma1athion 0.25 7 TalJ'! "Tciir 'PF'Tra'1.YcJ.t' t1 t> iJl! a.cnl "f'.t Ethyl 4-UthoJry'iJhényl 0.5 alatlon 0.5 Il, 5 Tonr 'PntY-l'IT" ychus hf.! "tacul (' lt'l a8 Ethyl 4-Phgnylphényi 0,5 - - 5'2 Tour Ana. 8 tristi 0 Malathion 4 '25 2813 Toiir Anasa tri sti Ethyl:

   4 Phé; tylghényl 0.5 MaJ.ath1on ü, 25 ¯ 32.4 Tour AnSS8 tri s.ti 00

  <Desc / Clms Page number 32>

   EXAMPLE V.-
In a series of new experiments a large number of N-mono-substituted alkyl dicarbamic acid esters are tested in combination with a series of phosphorus-containing acid derivatives. Tests against house flies by the turntable method are summarized in Table 8. Tests by the tower method against Epila-
 EMI32.1
 ohna varivestis and Tetranychus bimaculatus: 1iQE.it -: fntitj, .èl'iJ.él: f "da.lla Te àbl éàw 9.



   These combinations also exert a high degree of synergism.

  <Desc / Clms Page number 33>

 
 EMI33.1
 



  TJlJ3LEAU 8
 EMI33.2
 
 EMI33.3
 CarbaMate Phosphate Conc. (mg.1. conc, (?: 1 'u () T'i'; '1l .. + .t R ¯¯ 100 cd Nop.! 100 ç21 ± l-' Y.! JQ-ie 0'PSiial e.'J.1pt ¯i:! l¯C rclohex¯yI- ¯ ¯ '¯ IsoTironyl 500 - - PléltPf1u tour11311t .rusca dotrçsttcr 1 CYCI, r) b --VI C-41 / L 90 Pl a tN1l1 tour-art 'l1ca doinestJ¯ra 61 Cyclo1-} pxvl I Fonropif-1. 100 C-4l,? LI 2 (1 Pl ptPôl1 turning'; TllS ('ri c'iorttC \ tj ca 69 - - "ppra4 -Inîor 15 P111t <=> 1.J1l. t () 11T "nant. '' 'lJ (' A (1 ('\ 1"' rlI "'ti. (' a 55 C: rJ 1 '") 1, "' ':;. r1 l C' ('Ill1'ODVl 7 f) T'U' thvl Pa T'R thi.on 15 PlHt. "'11 turning -'u SCR rl (' \ T" 0ti ('[1 7 () P'l-} 'Y'; TJ ...., F ... t''1 y] SOO Pl rlt "é) l1 + - ') 111" "1; 1 .., 1-. <i <pQ- r1omti.cp - - - - - - - - - - - - ¯ ¯ ¯ ¯ ¯ - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - ('¯q.14 PO ^ -' a1-p ;:

  1J t0UT '"I' \ ant, HUSC8 n () '110tica. 51 rz'1 FthS'1 100 0-4? I? Li 20 Pl.8t.PôU turning, r'lA oOM12f; tlca 69 4-Illi- troryhenyl Ethyl 5000 - Plateau tou '! "' I1.ant? TUrca OO! '1I"'. tfca 8 - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - F, -1 Parat7nio,., 15 Tray turning r, osca ^ 3onestïc2 ¯ ¯ ¯ 4- :, -. "ojJhenyl EthY1 75 'Tethyl Parat" 1ion 15 Pl8teu ton-r'1.3nt finn-8tira 77 o-Chlo-ronl -). 1 ,,; l sopropy1 5000 - - Turntable "7lsr¯a coPSti ca 48 - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - B-? 1/199 50 Platau tou1 "'11ant' Í1Jsea domestica on 3-Chloro"!} h <? nYl I so-nropyl 250 B-21/199 50 Plet <:: au touraT1t ': USC8 (! omest1.ca 67 3-Trifluoro- Isopropyl 500 - - Turntable ";: usca dO!' 1r:> <:

  tica .. 20 1'lthyl!) hny1

  <Desc / Clms Page number 34>

 
 EMI34.1
 TABLE - 8 it e 1
 EMI34.2
 
 EMI34.3
 Carbamate Phosphatē¯¯¯¯ ..



  '"###########" Conc. (N.? ./.,; C, <1- = ;. / Mortality Conc. (-Mg.



  RR¯¯¯ 1¯00 c.¯3 "! ¯ Name 7.CO, wçm¯3¯ ythode ô'f2y¯ ± 3 ¯ f¯) ¯¯¯ ¯, ¯¯ - C-4124 0 Turntable rTusa . r7o! çf, i.ca 4. -q 1f - '' ifluaxo- Isopropyl 100 C-4124 20 Turntable Musca do3tica rethylhPnvl 5-Chlorophenyl -EthYlhēxvl¯ ¯ - 500 - ^ ¯ ¯ ¯ ¯ ¯ ¯ ¯ ¯ ¯ ¯ ¯ ¯ ¯ PlatAau-teurnnfi 'TlsCa-c7mrtica.¯ ^ ¯ 7, - ¯¯ R¯Z.f7.99 PO Plat-nii tiiir- "rt" " <= 'f'a -r <nnst; ¯cr 4 CI -Chlarah r5rl. 2 - F '.') '. T''vlhél 100 B¯' '',;

   0 Pl, c3.teqii turning 7'l-ieca rlo7l - tici. 61 'T: thvl Trathion 15 Turntable <i < <-c? ^ nt9.ca 1 5lch1oroph6nyl 2-Eth-tr h (:, - rl. 75 1éltliirl- Parathion 15 P.at ^ ao i-.oorar + "', ia'-n r'nc-tTr 77 Bzovl Isoo-ropyl 500 - - Turntable "'llSC?' '1r Fftj, c? ¯¯ ¯ ¯ ¯ ¯ ¯ ¯ ¯, ¯ ¯ ¯ ¯ ¯ ¯ ¯ - -¯ - -, tt .., 1 pprathion 15 Turning platpsu 'iio = ao "' -'-? t-! rp 4n 3nnr7¯ Iso.nropy, 1 75 Methyl Paa-ath4.on 15 Turntable Musca lr ^ sti.ca 5 .tt? rl Ft? wa 500 # # Platter turning M -Lisea domestica ¯ ¯ ¯ ¯ ¯ ¯ ¯ ¯ ¯- ¯ ¯ ¯ ¯ ¯ ¯ ¯ B-21/199 50 Platesu turning 1, uicp. domestica li4; iAt.hjrl EthzTl 250 B-21 / 1.99 50 Usca-oesticā¯¯¯70 turntable.



  Phenyl -FthTTlherl 5000 ¯ Turntable i3Tusca domeqtice 2 -. ---.-.-------- '-¯¯ ", -. - 14éthyi Parath, ion. 10 Turntable Musca do-est + ca, 13 ph ': nT, j¯ 2-Ethlhef. rl 50 Methyl Parathion 10 Musca turntable doeRtcp #### 30 ### .. "-''- ####### H -enyinexj - #### ###### B-31/199 ######## Turntable Musca à.omPstica 76 Phyl 2-Eth> + lhetryrl SOO B-21/199 40 Turntable "Tusea (cm-estica 48

  <Desc / Clms Page number 35>

 
 EMI35.1
 BOARD . 8 - (continued)
 EMI35.2
 C arbamate Phosphate Cano. (m. Cane. (f! l.g./ 111 "ortal Conc. (mµ. / Conc. (mg.1 irortali tF IL. R I0 em3 Nom- 1¯00 çmr¯ Test method ê.illt 24 h.



  , 4 - l1'tb-vlrhén, vl Iso "! 1ropyl 500 - - Turntable rfuca dornet: t.ca - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - Methy1 Parathion 10 Turntable luca dou1pQtica ::; 0 .--- iethylPYzény 1 Isopropy1 50 Methyl Parathior. 10 P'1 2teall tonrnart '' .1s ('P nom0ti C1't tif) B-2,1 / 199 4-0 Plateau tonr! 1ant' r ,, ( 'nomf "' t1 ('P 8 4-1 \ th \ 111rnyl l'sonropy1 2, OO B-21f199 4 0 Platef111 tot1T'TI1" nt iht1'! orst3ca 60 BenzT1 Ethyl 500 -,.

   PlRteE'.u turn! 1a'I'Jt 'fllSCCI c, - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - B-21/199 50 Turntable 'Íneé1 0ornr> sti.ca 65 Benzyl Ethyl 25Q B-21 / 199 50 Turntable n4usca <'! omE'tj.c? 90 - - - Diazinon 25 Turntable Husca don-esticn 46 Benzyl ¯ Bthy 1 125 Diazinon 25 Turntable 1 ', Tusce dompftic ?, in I:

  i4irfuryl Ethyl 500 - - Turntable 1-fli, .qca domestica 4 - - --- --- ---------- --------- ---- ------------- - ---- - - Diazinon 25 Turntable 1 \, fu8ca donieftica 48 Furfuryl Ethyl 125 Diazinon 25 P1atea11 turn dompstieq 60

  <Desc / Clms Page number 36>

   TABLE 9
 EMI36.1
 

  <Desc / Clms Page number 37>

   EXAMPLE VI.-
Other examples of synergistic combinations of organic esters of N-monosubstituted carbamic acids and in particular alkyl, alkenyl, aryl, aralkyl and heterocyclic esters with various derivatives of acids containing phosphorus and possessing insecticidal activity are given below. . Table 10 gives the results obtained on house flies by the turntable method.

   Table 11 gives results obtained against Epilachna varivestis, against Tetranyohus bimaculatus and against Anasa tristis.

  <Desc / Clms Page number 38>

 
 EMI38.1
 



  !! l3l: t! 2¯1Q-
 EMI38.2
 
 EMI38.3
 Carba.001at, Phosphate 6 Conc. (M, 7 / conc. Rti (r.1q.1 zip, ort? ''. It- zur, ... ¯¯ ¯¯.¯] .QQ¯ cm 5É Name J , 00¯ çrl # 1 -l tb r = PP d '= ss ai 8 <dd F-% fi4h. j "2µ) '1 mT + 1 - (7.-chJ¯oroYz'oyVl 500 - # Pl Ptppll tour1- = nt IfII8 (, Fi donpstica B-21 ,, / 1.99 50 P1:? t ^ t1 tr- ) llrnitit 11 r- nnm, fi.i cct -6 ïii. <.JT: 1 2- (l-chl.oro-orDyl) 250 bzz-1, / 199 50 Plateau toiirrant> '; iigca com ^ rt3 ca 5 # - C-4124 20 -P7.a''11 turning Ti il r -> domnticH 4p 'l- F rT; 1, 2 - (1, - ch l. O ron ropyi) 100 C-4124. 20 Plate-an t o 11 r-il î n t Musca domestica 59 Diazinon 25 Turntable r, friasca romnmtl, ci 25 P b;

  FnTrl 2- (1 - chlo roptonyl) 125 Diazinon 25 P3 atpau turning Musca flom m sti, c a Xi 'Allyl 500 Turntable 1 <Iusra rlomnptici ¯ ¯ ¯ ¯ ¯ ¯ ¯ ¯ ¯ B-21/199 50 Tray toumDrt Musca (1 0- (n 0 s ti. Ca 36 phnyï Allyl z50 B-81/199 50 Turntable Musca domestica si Diazinon 25, Turntable Musca domestica 22 "li. Eny], à.I l, 3rl 125 Di azinon. 25 Turntable" (ll s C a Cl O'QI QS tÉ- C 8 7 8 - Methyl Parathion 15 Turntable Mu3ca omestLca . 4cl é> ii. "Ijri A],] yl 125 Methvl Parathion 15 Turntable îlusca r'omcstica ¯¯77¯¯¯ '' r / 1 Circ?, NÎ *> - 1r], 500 # - Turntable rvsoa 40u0ert3-ro 10 ¯ ¯ Mpth '"'! pa% o + aflro, J 15 Plateau tmi? t1 = 801'i 1? iis = a nr7rnnri'.i Gx 5X '' ';, 2ï'.

   (trC''31 ', o.;. sr1 75 "o -'-. hl P.'" "'pthion 15 Pla - ?? u + r-111rT-ianl:' T17SC 7r? '!' 'xfz. C3 li

  <Desc / Clms Page number 39>

   TABLE 10 (continued)
 EMI39.1
 
 <tb> Carbamate; <SEP> Phosphate
 <tb> R4 <SEP> Conc. (Mg / <SEP> Conc. <SEP> (mg. <SEP> Mortality
 <tb>
 
 EMI39.2
 R # ¯ 100-Qm ± L Nom 100 cm3). Method c es sai Subject .ê P12! - {L.



  Bthv1 2-Naphtyl 500 - - Turntable "liisca dompstj l1 - - î '...... ¯ ¯" - Turntable "usca domUce ##, - ## f, t-)' - B -21/199 50 Turntable tourrart 1U8 ('a n01Tlesttcé1 5 thy1' -marhthyl 250 B-21/199 50 Turntable l'T11 ('a 0 (' r (,., ('Ti C'R 7s Ethy1 ¯ ¯ ¯'BenzT'i- ¯ - 500 - - Flat '? C! L1 tourrJant j1Tl1 (, é1 nOfl1Pt:

  t ('a 8 - Methyl Parathion 15 Turntable Hll!' 1CR c '! o "l0stica 5
 EMI39.3
 
 <tb> Ethyl <SEP> Benzyl <SEP> 75 <SEP> Methyl <SEP> Parathion <SEP> 15 <SEP> Plateau <SEP> turning <SEP> Musca <SEP> domestica <SEP> 72
 <tb> Phenyl <SEP> Benzyl <SEP> 500 <SEP> - <SEP> - <SEP> Plateau <SEP> turning <SEP> Musca <SEP> domestica <SEP> 4
 <tb>
 
 EMI39.4
 - - - Diazinon ¯ ¯ ¯25 ¯ ¯ 'Turntable Musca r'onpptica' '46 Phenyl Benzyl 125 Diazinon 25 Turntable Musca 00TrlPstica se - - y¯ B-21/199 50 Turntable' vzsc2 1o "'1C'sti ca 81 Vf Ph4njrl Benzyl 250 B-21/199 50 Turntable T" Íl1 (' domestica 95 Furfuryl Benzyl 500 - - Turntable l 'uqca àOTTlpstj ca 2 - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - Diazinon 20 Tray turning Mupca d01jTsti ('48 Furfuryl Benzyl' 100

  Diazinon 20 Turntable "1usca (] oT'1" '! Tica 68
 EMI39.5
 
 <tb> - <SEP> - <SEP> C-4124 <SEP> 15 <SEP> Plateau <SEP> turning <SEP> Musca <SEP> domestica <SEP> 55
 <tb> Furfuryl <SEP> Benzyl <SEP> 75 <SEP> C-4124 <SEP> 15 <SEP> Plateau <SEP> turning <SEP> Musca <SEP> domestica <SEP> 76
 <tb>
 
 EMI39.6
 Phenyl Piperonyl 500 - - Turntable lfusca domestiea 2
 EMI39.7
 
 <tb> - <SEP> - <SEP> C-4124 <SEP> 15 <SEP> Plateau <SEP> turning <SEP> Musca <SEP> domestica <SEP> 26
 <tb> Phenyl <SEP> Piperonyl <SEP> 75 <SEP> C-4124 <SEP> 15 <SEP> Plateau <SEP> turning <SEP> Musca <SEP> domestica <SEP> 36
 <tb>
 

  <Desc / Clms Page number 40>

   TABLE 10 (continued)
 EMI40.1
 
 <tb> Carbamate <SEP>, Phosphate
 <tb>
 
 EMI40.2
 Cono. (mg! Cone. (MgI M 0 r t 1 t R6 oq- ± m ± L- - lOO cm3L Mé! hQ. ± ssa1 Subject¯ çn 4¯h, ..
 EMI40.3
 
 <tb>



  ---- <SEP> - <SEP> Diazinon <SEP> 20 <SEP> Plateau <SEP> turning <SEP> Musca <SEP> domestica <SEP> 14
 <tb>, Phenyl <SEP> Piperonyl <SEP> 100 <SEP> Diazinon <SEP> 20 <SEP> Plateau <SEP> turning <SEP> Musca <SEP> domesti <SEP> ca <SEP> 29
 <tb>
 <tb>
 
 EMI40.4
 - - B-21 / l99 40 Turntable Musea dompstica 40
 EMI40.5
 
 <tb> Phenyl <SEP> Piperonyl <SEP> 200 <SEP> B-21/199 <SEP> 40 <SEP> Plateau <SEP> turning <SEP> Musca <SEP> domestica <SEP> 54
 <tb> Ethyl <SEP> 4-Methylumbelliferonyl <SEP> 500 <SEP> ---- <SEP> Plateau <SEP> turning <SEP> Musca <SEP> domestica <SEP> 4
 <tb> -
 <tb> ---- <SEP> - <SEP> Methyl <SEP> Parathion <SEP> 10 <SEP> Plateau <SEP> turning <SEP> Musca <SEP> domestica <SEP> 46
 <tb>
 
 EMI40.6
 Eth,

  yl 4-1ethylunibelli-
 EMI40.7
 
 <tb> feronyl <SEP> 50 <SEP> Methyl <SEP> .Parathion <SEP> 10 <SEP> Plateau <SEP> turning <SEP> Musca <SEP> domestica <SEP> 96
 <tb> Phenyl <SEP> Trichloroethyl <SEP> 500-- <SEP> - <SEP> Plateau <SEP> turning <SEP> Musea <SEP> domestica <SEP> 4
 <tb>
 
 EMI40.8
 - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - C-4124 20 Flusca dOJ'llP turntable:

  '1ti.ea 53 Phenyl Tr1ohloroethyl 100 C-4124 2Q Turntable' usea dom0stica B7
 EMI40.9
 
 <tb> ---- <SEP> Diazinon <SEP> 25 <SEP> Plateau <SEP> turning <SEP> Musca <SEP> domestica. <SEP> 26
 <tb> Phenyl <SEP> Trichloroethyl <SEP> 125 <SEP> Diazinon <SEP> 25 <SEP> Plateau <SEP> turning <SEP> Musea <SEP> domestica <SEP> 40
 <tb>
 

  <Desc / Clms Page number 41>

   TABLE 11
 EMI41.1
 
 EMI41.2
 
 <tb> Carbamate <SEP> Phosphate <SEP>, <SEP>
 <tb> Cond. <SEP> Conc.

    <SEP> Quantity
 <tb> 4 <SEP> R6 <SEP> Powder <SEP> Powder <SEP> (books / <SEP> Method <SEP> Mortality
 <tb> R- <SEP> R @ <SEP> (%) <SEP> Name <SEP> (%) <SEP> acre) <SEP> test <SEP> -, test <SEP> (%)
 <tb> Ethyl <SEP> 2-Naphthyl <SEP> 1 <SEP> - <SEP> - <SEP> 22.2 <SEP> Tour <SEP> Epilachna <SEP> varivestis <SEP> 0
 <tb> - <SEP> - <SEP> - <SEP> Malathion <SEP> 0.5 <SEP> 19.8 <SEP> Tour <SEP> Epilachna <SEP> varivestis <SEP> 5
 <tb> Ethyl <SEP> 2-Naphthyl <SEP> 1 <SEP> Malathion <SEP> 0.5 <SEP> 19.0 <SEP> Tour <SEP> Enilachna <SEP> varivestis <SEP> 100
 <tb> Phenyl <SEP> Benzyl <SEP> 1 <SEP> - <SEP> - <SEP> 32.7 <SEP> Tour <SEP> Epilachna <SEP> varivestis <SEP> 0
 <tb>
 
 EMI41.3
 - - - Mal a tbi on 0, 5 25.9 Tour Epilactma varivesti s 30
 EMI41.4
 
 <tb> Phenyl <SEP> Benzyl <SEP> 1 <SEP> Malathion <SEP> 0.5 <SEP> 28,

  3 <SEP> Tour <SEP> Epilachna <SEP> varivestis <SEP> 90
 <tb> Ethyl <SEP> Furfuryl <SEP> 1. <SEP> - <SEP> - <SEP> 24.7 <SEP> Tour <SEP> Epilachna <SEP> varivesti <SEP> s <SEP> 0
 <tb> - <SEP> - <SEP> Malathion <SEP> 0.5 <SEP> 19.8 <SEP> Tour <SEP> Epilachna <SEP> varivestis <SEP> 24
 <tb> Ethyl <SEP> Furfuryl <SEP> 1 <SEP> Malathion <SEP> 0.5 <SEP> 20.7 <SEP> Tour <SEP> Epilachna <SEP> varivestis <SEP> 98
 <tb> Ethyl <SEP> Furfuryl <SEP> 1 <SEP> - <SEP> - <SEP> 6.9 <SEP> Tour <SEP> Tetranychus <SEP> bimaculatus <SEP> 4
 <tb> Ethyl <SEP> Malathion <SEP> 0.5 <SEP> 6.4 <SEP> Tour <SEP> Tetranychus <SEP> bimaculatus <SEP> 28
 <tb> Ethyl <SEP> Furfuryl <SEP> 1 <SEP> Malathion <SEP> 0.5 <SEP> 5.3 <SEP> Tour <SEP> Tetranychus <SEP> bimaculatus <SEP> 61
 <tb> Phenyl <SEP> Trichloroethyl <SEP> 1 <SEP> - <SEP> - <SEP> 9,

  3 <SEP> Tour <SEP> Tetranychus <SEP> bimaculatus <SEP> 0
 <tb> ---- <SEP> - <SEP> Malathion <SEP> 0.5 <SEP> 8.0 <SEP> Tour <SEP> Tetranychus <SEP> bimaculatus <SEP> 59
 <tb> Phenyl <SEP> Trichloroethyl <SEP> 1 <SEP> Malathion <SEP> 0.5 <SEP> 8.3 <SEP> Tour <SEP> Tetranychus <SEP> bimaculatus <SEP> 97
 <tb>
 
 EMI41.5
 Ethyl 1-:

  Naph thyl 0.5 - - 2.9 Tower Anasa tri.stis 0
 EMI41.6
 
 <tb> - <SEP> Malathion <SEP> 0.25 <SEP> 27.8 <SEP> Tour <SEP> Anasa <SEP> sort <SEP> sti <SEP> s <SEP> 0
 <tb>
 
 EMI41.7
 Ethyl 1-Iahthyl a, 5 Malathion 0.5 27, Tour Anasa tristis 90

  <Desc / Clms Page number 42>

   TABLE 11 (continued)
 EMI42.1
 
 <tb> Carbamate <SEP> Phosphate
 <tb> Conc. <SEP> Cone.

    <SEP> Quantity
 <tb> 4 <SEP> Powder <SEP> Powder <SEP> [drunk! <SEP> Method <SEP> Mortality
 <tb>
 
 EMI42.2
 R R z Name ¯ ± ± [¯ acre) diesel 2g1 ¯-1L¯Ethyl 1-Naphthyl 0.5 - - 9.1 Tower Tetrrrlychus bimaculatus 8
 EMI42.3
 
 <tb> - <SEP> - <SEP> - <SEP> Malathion <SEP> 0.25 <SEP> 13.7 <SEP> Tour <SEP> Tetranychus <SEP> bimaculatus <SEP> 34
 <tb> Ethyl <SEP> 1-Naphthyl <SEP> 0.5 <SEP> Malathion <SEP> 0.25 <SEP> 10.5 <SEP> Tour <SEP> Tetranychus <SEP> bimaculatus <SEP> 100
 <tb> Ethyl <SEP> 2-Naphthyl <SEP> 1.0 <SEP> - <SEP> - <SEP> 51.4 <SEP> Tour <SEP> Anasa <SEP> tristis <SEP> 0
 <tb> - <SEP> - <SEP> - <SEP> Malathion <SEP> 0, <SEP> 25 <SEP> 46.2 <SEP> Tour <SEP> Anasa <SEP> tristis <SEP> 0
 <tb> " <SEP> Ethyl <SEP> 2-Naphthyl <SEP> 0, <SEP> 5 <SEP> Malathion <SEP> 0, <SEP> 25 <SEP> 45,

  6 <SEP> Tour <SEP> Anasa <SEP> sort <SEP> sti <SEP> s <SEP> 90
 <tb> Furfuryl <SEP> Benzyl <SEP> 0.5 <SEP> - <SEP> - <SEP> 22.0 <SEP> Tour <SEP> Tetranychus <SEP> bimaculatus <SEP> 2
 <tb> - <SEP> ---- <SEP> Malathion <SEP> 0.25 <SEP> 26.5 <SEP> Tour <SEP> Tetranychus <SEP> bimaculatus <SEP> 70
 <tb> Furfuryl <SEP> Benzyl <SEP> 0.5 <SEP> Malathion <SEP> 0.25 <SEP> 19.5 <SEP> Tour <SEP> Tetranychus <SEP> himaculatus <SEP> 100
 <tb> Ethyl <SEP> 2-Ethylhexyl <SEP> 1.0-- <SEP> - <SEP> 25.9 <SEP> Tour <SEP> Anasa <SEP> tristis <SEP> 10
 <tb> - <SEP> ---- <SEP> Malathion <SEP> 0.25 <SEP> 46.6 <SEP> Tour <SEP> Anasa <SEP> tristis <SEP> 0
 <tb> Ethyl <SEP> 2-Ethylhexyl <SEP> 1.0 <SEP> Malathion <SEP> 0.5 <SEP> 27.5 <SEP> Tour <SEP> Anasa <SEP> tristis <SEP> 90
 <tb> Furfuryl <SEP> 2-Ethylhexyl <SEP> 0.5 <SEP> - <SEP> - <SEP> 15,

  8 <SEP> Tour <SEP> Tetranychus <SEP> bimaculatus <SEP> 2
 <tb> - <SEP> - <SEP> - <SEP> Malathion <SEP> 0.25 <SEP> 25.4 <SEP> Tour <SEP> Tetranychus <SEP> bimaculatus <SEP> 41
 <tb> Fiirfuryl <SEP> 2-Ethylhexyl <SEP> 0.5 <SEP> Malathion <SEP> 0.25 <SEP> 19.3 <SEP> Tour <SEP> Tetranychus <SEP> bimaculatus <SEP> 87
 <tb> Furfuryl <SEP> 2- (1-Chloropropyl) <SEP> 0.5 <SEP> - <SEP> - <SEP> 23.3 <SEP> Tour <SEP> Tetranychus <SEP> bimaculatus <SEP> 4
 <tb> Malathion <SEP> 0.25 <SEP> 25.4 <SEP> Tour <SEP> Tetranychus <SEP> bimaculatus <SEP> 41
 <tb> Furfuryl <SEP> 2- (1-Chloropropyl) 0.5 <SEP> Malathion <SEP> 0.25 <SEP> 21.7 <SEP> Tour <SEP> Tetranychus <SEP> bimaculatus <SEP> 77
 <tb> Phenyl <SEP> Trichloroethyl <SEP> 1.0 <SEP> - <SEP> - <SEP> 47.6 <SEP> ' <SEP> Tour <SEP> Anasa <SEP> tristis <SEP> 0
 <tb> - <SEP> - <SEP> Malathion <SEP> 0.5 <SEP> 51,

  9 <SEP> Tour <SEP> Anasa <SEP> tristis <SEP> 0
 <tb> Phenyl <SEP> Trichloroethyl <SEP> 1.0 <SEP> Malathion <SEP> 0.5 <SEP> 45.6 <SEP> Tour <SEP> Anasa <SEP> tristis <SEP> 90
 <tb>
 

  <Desc / Clms Page number 43>

 EXAMPLE VII. -
Cn tests a number of organic esters of N, N-disubstituted carbamic acids and in particular of substituted alkyl, alkenyl, aryl and aryl esters in combination with various acid derivatives containing exerting phosphorus. insecticidal activity as indicated below. Table 12 summarizes the results obtained on house flies by the turntable method and Table 13 shows the results of the tower method on various crop insects and spiders.



   These combinations all exert a marked synergistic effect.

  <Desc / Clms Page number 44>

 



    TABLE --the
 EMI44.1
 
 EMI44.2
 
 <tb> Carbamates <SEP>, <SEP> Phosphate
 <tb> Conc. <SEP> (mg./ <SEP> Conc. (Mg./
 <tb> R4 <SEP> R5 <SEP> R6 <SEP> 100 <SEP> cm3) <SEP> 100 <SEP> cm3) <SEP> Morality
 <tb>
 
 EMI44.3
 HE. R B- bzz Name ----- Methon.! Ld'e ê1ûet ¯en 24¯h.
 EMI44.4
 
 <tb>



  Methyl <SEP> Methyl <SEP> Phenyl <SEP> 500 <SEP> - <SEP> - <SEP> Plateau <SEP> turning <SEP> Musca <SEP> domestica <SEP> 4
 <tb>
 <tb> - <SEP> Diazinon <SEP> 25 <SEP> Plateau <SEP> turning <SEP> Musca <SEP> domestica <SEP> 42
 <tb> Methyl <SEP> Methyl <SEP> Phenyl <SEP> 125 <SEP> Diazinon <SEP> 25 <SEP> Plateau <SEP> turning <SEP> Musca <SEP> domestica <SEP> 62
 <tb> Methyl <SEP> Methyl <SEP> 3-Chlorophenyl <SEP> 500 <SEP> - <SEP> - <SEP> Plateau <SEP> turning <SEP> Musca <SEP> domestica <SEP> 4
 <tb>
 
 EMI44.5
 '' * '' '' '**' '' '*' '' '' '' * '' '*' '' '' '* -' "'* -''------- ------------------. - <# -------.
 EMI44.6
 
 <tb>



  - <SEP> Methyl <SEP> Parathion <SEP> 15 <SEP> Plateau <SEP> turning <SEP> Musca <SEP> domestica <SEP> 74
 <tb> Methyl <SEP> Methyl <SEP> 3-Chlorophenyl <SEP> 75 <SEP> Methyl <SEP> Parathion <SEP> 15 <SEP> Plateau <SEP> turning <SEP> Musca <SEP> domestica <SEP> 82
 <tb> Methyl <SEP> Methyl <SEP> 4-Chlorophenyl <SEP> 500 <SEP> - <SEP> - <SEP> Plateau <SEP> turning <SEP> Musca <SEP> domestica <SEP> 2
 <tb>
 
 EMI44.7
 - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - ¯ ¯ ¯ ¯ ¯ - B-21/199 50 Turntable 1ùsca domestica 63
 EMI44.8
 
 <tb> Methyl <SEP> Methyl <SEP> 4-Chlorophenyl <SEP> 250 <SEP> B-21/199 <SEP> 50 <SEP> Plateau <SEP> turning <SEP> Musea <SEP> domestica <SEP> 72
 <tb> - <SEP> C-4124 <SEP> 20 <SEP> Plateau <SEP> turning <SEP> Musea <SEP> domestica <SEP> 76
 <tb> Methyl <SEP> Methyl

   <SEP> 4-Chlorophenyl <SEP> 100 <SEP> C-4124 <SEP> 20 <SEP> Plateau <SEP> turning <SEP> Musca <SEP> domestica <SEP> 84
 <tb> - <SEP> Diazinon <SEP> 25 <SEP> Plateau <SEP> turning <SEP> Musca <SEP> domestica <SEP> 42
 <tb> Methyl <SEP> Methyl <SEP> 4-Chlorophenyl <SEP> 125 <SEP> Diazinon <SEP> 25 <SEP> Plateau <SEP> turning <SEP> Musea <SEP> domestica <SEP> 62
 <tb> - <SEP> Methyl <SEP> Parathion <SEP> 15 <SEP> Plateau <SEP> turning <SEP> Musca <SEP> domestica <SEP> 74
 <tb> Methyl <SEP> Methyl <SEP> 4-Chlorophenyl <SEP> 75 <SEP> Methyl <SEP> Parathion <SEP> 15 <SEP> Plateau <SEP> turning <SEP> Musea <SEP> domestica <SEP> 86
 <tb> Phenyl <SEP> Phenyl <SEP> Ethyl <SEP> 500 <SEP> ---- <SEP> Plateau <SEP> turning <SEP> Musca <SEP> domestica
 <tb>
 
 EMI44.9
 - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - -

  

  <Desc / Clms Page number 45>

   TABLE 12 (continued)
 EMI45.1
 
 <tb> Carbamates <SEP> Phosphate
 <tb>
 
 EMI45.2
 Conc. m Cone (M Method '' I'orta? īt A5 A6 100 cr3 Name 100 Lm3e diessai. Su and iiÉ) li] 1 ¯
 EMI45.3
 
 <tb> - <SEP> C-4124 <SEP> 20 <SEP> Plateau <SEP> turning <SEP> Musca <SEP> domestica <SEP> 55
 <tb>
 
 EMI45.4
 Phcnvi Phenyl Ethyl 100 C-4124 20 Turntable Iusca omestica 08
 EMI45.5
 
 <tb> Methyl <SEP> Parathion <SEP> 15 <SEP> Plateau <SEP> turning <SEP> Musca <SEP> domestica <SEP> 39
 <tb> Phenyl <SEP> Phenyl <SEP> Ethyl <SEP> 75 <SEP> Methyl <SEP> Parathion <SEP> 15 <SEP> Plateau <SEP> turning <SEP> Musca <SEP> domestica <SEP> 56
 <tb> Methyl <SEP> Phenyl <SEP> Isopropyl <SEP> 500 <SEP> - <SEP> Plateau <SEP> turning <SEP> Musca <SEP> domestica <SEP> 6
 <tb> - <SEP> - <SEP> C-4124 <SEP> 20 <SEP> Plateau <SEP> turning

   <SEP> Musca <SEP> domestica <SEP> 51
 <tb>
 
 EMI45.6
 Methyl Phenyﯯ¯¯¯¯Isoro-1 100 C-4124 20 Turntable Musca domestica 66 Methyl 3-Chlorophenyl Isopr.opyl 500 - - Turntable ifusca domestica 1-3 * '' * '' '' ** '' '' * '' '' '*' '*' '' '' * '' ** "''" -''-'---'------------- ---- - # -------- ---
 EMI45.7
 
 <tb> Methyl <SEP> Parathion <SEP> 15 <SEP> Plateau <SEP> turning <SEP> Musca <SEP> domestica <SEP> 47
 <tb> Methyl <SEP> 3-Chlorophenyl <SEP> Isopropyl <SEP> 75 <SEP> Methyl <SEP> Parathion <SEP> 15 <SEP> Plateau <SEP> turning <SEP> Musca <SEP> domestica <SEP> 76
 <tb> Methyl <SEP> 5-Chlorophenyl <SEP> Allyl <SEP> 500 <SEP> - <SEP> Plateau <SEP> turning <SEP> Musca <SEP> domestica <SEP> 4
 <tb> Methyl <SEP> Parathion <SEP> 15 <SEP> Plateau <SEP> turning <SEP> Musca <SEP> domestica <SEP> 47
 <tb> Methyl <SEP> 5-Chlorophenyl <SEP> Allyl <SEP> 75 <SEP> Methyl <SEP>

  Parathion <SEP> 15 <SEP> Plateau <SEP> turning <SEP> Musca <SEP> domestica <SEP> 63
 <tb> - <SEP> Diazinon <SEP> 25 <SEP> Plateau <SEP> turning <SEP> Musca <SEP> domestica <SEP> 46
 <tb> Methyl <SEP> 5-Chlorophenyl <SEP> Allyl <SEP> 125 <SEP> Diazinon <SEP> 25 <SEP> Plateau <SEP> turning <SEP> Musca <SEP> domestica <SEP> 62
 <tb>
 
 EMI45.8
 ## '"', <-. '"' B-31/199 50 Turntable Musca domestica 70
 EMI45.9
 
 <tb> Ethyl <SEP> 5-Chlorophgnyl <SEP> Allyl <SEP> 250 <SEP> B-21/199 <SEP> 50 <SEP> Plateau <SEP> turning <SEP> Musea <SEP> domestica <SEP> 87
 <tb>
 

  <Desc / Clms Page number 46>

 
 EMI46.1
 TABLE 1? ùggitel
 EMI46.2
 -. # .... # -. ## CarbaBatps¯¯¯¯¯¯¯, ¯¯¯¯¯ ## Phosphate.¯¯¯ 1, ° R5 R6 Conc. (mg. / "Conc.

   (m g. f - .¯..¯, -. ¯ 100 cms) Nom¯: L00 ^ çm) ¯¯¯?.? µ tho ô,; d. 'egg # 1 and 2 "J: -' 'thy Eth-yl Ph (' -" - nyl 500 ¯ ¯ ¯ Turntable Musca domestica 7TT'ri - B-I199 40 Turntable Musca domestica 49 1 Ethyl Phényi 200 B -2.199 40 Turntable li-isca, lomet: Cc3. 60 n-rroPyl n-ProFy1 Phényl 500 Turntable husca cameçt3.ci:

   - - ¯ ¯ ¯ ¯ ¯ T ¯ r mr,, ¯ .. ¯ ¯ ¯ r ¯ ¯ ¯ ¯ w. . - - - - .. ¯ ¯ r ¯ r r r .r - -. r ¯., r - - ... r ..w - - - - - B-21/199 40 Turntable rillsca fIn'u-stici 48 r -P î, 0 n7ri. n-Propyl Phenyl 200 B-21 / lg9 40 Turntable Pusea ramesti.ci. 60 - n: Propyl Phenyï - 1.lôthyl Parathion 10 Pl.ateau tourna-nt 8111sca romPSti.c-i '.. 24 n-Pr.a; i, y1 n -P ropyl Phenyl 50 lî'thyl Parathion 10 Turntable Fiusca flommstici 40 i-, nv 1 Phén7îl phenol 500 Plat (-, at the turn rfusca domesti.a3. 5 - - - - - B - 21/1 9 9 40 Turntable Musca ciompftiot 30r? 1 4 thyl Phenyl Phényl 200 BP.Ifl99 40 Turntable Musca domestici 46 - - - - Diazinon 20 Turntable Musca r3.omestLci 1.9.-1 Phenyl.

   Phenyl 100 Diazinon 20 Turntable Musca doniestici 36

  <Desc / Clms Page number 47>

 
 EMI47.1
 TABLE 13
 EMI47.2
 
 EMI47.3
 Carbamates Phosphate 5 Conc. Cone. Ouantitg R¯- B¯- R Powder rlam Powder i1iYL2. !: o - :: - toJi t- <OEj ù '+ l. Î -. -) -l¯- t. Oq s ai Nut -¯¯i :: l¯¯- é t-li 7 1 Methyl Pheny1 6.1 Ta7ù7r ---- Tetrany'êTi'7s-TDii-maculatus 2 - - Malathion 0, 5 3, 4 Tour Tetranychus bimaczzlatus 13,> thy1 Methyl Phenyl 1 Malathion 0.5 3? Tower Tetranychus binlacu1atus 1 (0 e thrl # L6tlnirl.

   Phenyl 1 - 6 8 Tour?. Turqantia hiq triorica 0 - Malathion 0.5 19.6 Tour l \ .fu1: 'gantia h1.t1 "īf) Yltca 90 1'T4thyl Methyl Phenyl Malathion 0.5 2Q, 7 Tour "'urgantia hitrioJ'1ica 95 \ / f pth; rl FI4thyl 3-Chlorophenyl 1 - 6,0 Tozr¯ Tetran; r (' hl1S bimacffl-ati-is 6 th. - Malathion 0,5 7,2 Tour TÓt1 "nnychus bimaculatus 28 H t! 'Lyl" .1 X thyl 3-Ch1orop-hény1 1 Ma3athion 0.5 4,7 Toiir Tetran; rr-hus bimacu18-tu 93 "1 É th, irl Methyl 4-Chlorophenyl 1 - - - 15, Tour Epilae} ll1R varivQrti 0 - Malathion 0.5 10.2 Tour Epilaehna va ri va? Fi 5 7> 6 tlçrl jlé thyl 4-Chloro19'hényl 1 11alathion 0.5 6.5 Tour Enil- achna vnrivcstis 80 ù.ifthjrl 'léthyrl 4-Chlorophényl 5,1 Tour Tetramyrchus bimaculatvs, .l é, th, r 1,111 ethyl 4-Chlorophény1 5,1 Tour Tetral1yehus bi.macu1atlls - - Ualathion 0,5 6,4 Tour T etr an7f cb liq bim a cui, atu s 9 -i6th;

  -1 1 <i é thyrl 4-Ch1orophény1 1 Mal a. thi on 0.5 4.9 Tower Tetr¯ apyClluS bimaculatus 100 Isopro-'ly1 Isopropy1 Ethyl 1 - - 16.6 Tower Tetranychizr, bimaculatus - .7, lalathion 0.5 16, 6 Tower Tetranychus bimaculatus 57 1 sop ro pyi Isopropyl Ethyl 1 Malathion 0, 5 16, 6 Tour T e tr am y chus bima c1a? atus 68. ? 'éth; rl P h Fnjrl Iqooropyl 1 - - 16.4 Tower Tetranychus bimacul3.tus 0 -: 1tIala thion 0, 5 PO> 7 Tower Tetranychus bimacul; 1 V.1S 28' .ié th, Tl Phenyl l SODl'omT1 1 f! A1athion 0, 5 13.2 Tour Tetranychus bim acul. atus 67

  <Desc / Clms Page number 48>

 
 EMI48.1
 TABLFAÜ 1¯, soot,
 EMI48.2
 Carbamates pn0rhate 1. ############# Conc. Conc. Ouantitë allo cal 5 6 Powder Powder (1, iv; rs, / T0tÏ1 () '' '0 ioi ia.li t .t2-- Ru R- fil nQ!) 1- ¯fiL- ¯9 &! SÙ-- s : 12f.ei .:; and ¯¯.I% ¯¯¯.



  '; é f lxjrl Methyl Phenyl 0,5 '# - 279 Tour J .. "f1f -' (la + ri st 1 - Methyl Phenyl Malathion 0,25;? 6,0 Tour iira ra tr4 ti sr # S-thy7 .. 1ethyl Phenyl 0.5 Malathion 0,? 5 z 5, 9 Round A> 1: 1.: "N tT'i '"' tj8 1011 Etl: 1Yl ^ thyl Phnyl 0, 5 ¯¯ ¯¯ 49, 5 Taur A ,, 4 a - ,,, r: i .-. T 0 - - - - Malathion 0, 5 46, 6 Tour; \ '1 [1. "[1 tT';" 'U8 i0 Ethyl Ethyl Phenyl 0, 5 Malathion 0, 25 45.4 Tour Ar <1Sel a t ri, s t 1-, - 0: '1 thy3:

   Ethyl Phenyl 0, 5 - - 10.0 Tour Tct-'r> ,, z = ciZtm bl111aCl1J.A.t118 0 - - - Malathion 0.25 1? O Tour Tptrllrcl11JS btmaenletus 14 F'til7rl Ethyl Phenyl 0.5 Malathion 0.25 6.5 Tour 8trnvchl1 hirTléJC111at ",. 73 n-Nroyl n-Propyl Phenyl 0.5 - - 21.5 Tour 'l'etraYlycl1.1: 1.S biI1l"' C1Üa + l1CJ fi - - - - Malathion 0.25 25.7 Tour 'l'f:'; r [1nyc111 hi.YTJ [I ('111atl1s PO n-Propyl ¯n-Proyl Phenyl 0.5 Ma1athion 0.5 20.4 Tour rp + T '[1, ..' '' nl1f '; ¯5ac,.?, A1, 9 ir at miiri Phény1 Phény1 0.5 7.1.3 rp "" 11T' 1 "f1 ", -" "" '' '' "'' r, ...} ,,, bi.1" ('11!. "\ tns 3 - Phenyl #' - Malathion 0.25 10.7 Round Tr, tr, rr? U birr8.C1.1l., TllP 9 ', r: -t1-: 1yl Phenyl Phénvl oye5 Malathion 0.25 Il ,? Tour' J't'Y '' "1'1ycll1'tf \ h:

  t5- "ar, i.at" s 11 '", z'htTl Phnyl Phenyl 0, 5 ¯¯ ¯¯ 5 5, o, - Y1rr. fr i. s ti U fl - - Malathion 0.25 4G , 6 1 --u = 8.? Sa tre # + 1 I n = 'ét1.v1 P h 4nyrl Phenyl 0.5 Malathion 0.25 Q66 Tour ArftPA. -R ti.r 60 i,: r + '11: Tl 'ethZr7.'. ¯ 3-Chloronhenyl 1,0 - - 2tu4 T011T 'p .. "' lc:! R1 t'Y '; f1ti.



  - - - Q, le.lath3, or 0, 5 27.8 Turn> 1? ? ? 1 "7 1 r + <T ('thy1 Methyl 3-Chlo'! 'Opbenyl. 1, 0 Malathion 0, 25 28.9 Tour JI. "18f1> + -1 Cit 1 1 C é 1éthvl Methyl 4-Chl.orophenyl 1.0 - - 45.8 1 "f101J '!' A" 'IP:' 8 a + ri, r +5 p.



  - -ri - - leo Malathion 0, 46.6 T0111 'Anapa' + 1.s ± '.a' 'T''l, 0 1 thyme Methyl 4-Chlorophenyl 1.0 Malathion 0.5 47, 1 Tristi Tower. 92

  <Desc / Clms Page number 49>

   EXAMPLE VIII.-
Other examples of synergistic combinations of organic esters of N, N-disubstituted carbamic acids, where the N, N disubstitute is of the divalent alkyl or alkyloxy-alkyl type, with a variety of phosphorus-containing acid derivatives exerting a insecticidal activity are given below. Table 14 gives the results obtained on house flies by the turntable method. Table 15 gives the results of the sprinkling rounds on different crop insects and spiders.

  <Desc / Clms Page number 50>

 
 EMI50.1
 



  ARRAY ¯1¯4
 EMI50.2
 
 EMI50.3
 Carbamates Phosphate "Conc. (M. / Conc. (M /] 'fO 1" tE'J.; Tee in 1¯- R 100¯cm5l¯¯ Name 100¯gm ± l- Mptho: 2.e ... 9.g ± .ê.9j ,. 6.El: t. -..'''... '2 ..- ..



  And' <1yle: ne oxy- Ph4nyrl 500 - - Turntable 'Jf10F1 0r) Yf1psti. (!;: "' T 5rlô, '1e - - - Mêthyl Parathion 10 Plate tC11l1" n P.11 t "[ 118 ('[1 n (' 1Y! F '> ti C'r SR? T1: 1' \ Tl.ène oi-T4th / Tléne Phényl 50 Mêthyl PI11: '8.tl'don 10 Pl.atec311 tour' ' ! (1 '' '' t. R ,, ('q rol "0" 1ti.c 4s - "- - C-4124 15 P], rtraii turning' 1, isPr tln" 1 "sti N1 5 F't1tvHme ph6 - T.rl 75 c-4124 15 Plf1t0r: 1ll tr) 11T '' 'B "t M'1r -' ('nnYl, (,, ti N' B? <oX'lyéthv19ne ,, - '- - B-M / 199 40 .o a'! .. r11 tnll1: "" p.1 "'+:

   l \ J1 ",, (10r ,, 0Rtj Cf. 1 5 tr1'lTl '1e Php.l1yl 200 B-21/199 40 Turntable Musca fiorqo <tica 0 oxàiôtbv14ne - Diazinon 20 Turntable Ï'Iuf'R. 00r10Pti ca 4P EtyJ.9ne or0thylne Pheny1 100 Diazinon 20 Turntable 1I, TusC'a <'Iorqp :: 1tica 50 Tetra- Phenyl 500 .I- "- - Turntable 1 <Tus = a domestica methylene - - - {Ótl1yl Parathion 10 Turntable Musca dor.tpsti.ca 30 Tetra- Phenyl 50 Mêthyl Parathion 10 Turntable Musca à011'lPt: tca 48 i64thylëne

  <Desc / Clms Page number 51>

 
 EMI51.1
 ? ABLEAU l4sui.te)
 EMI51.2
 Carbarnates Phosphate r "# '" ###### "## .............. ## - ###### - ######### - #. #### - '6 Conc. (Mg./ No¯ Conc.

   (mg. / Mortality ¯1tl fl- 100 cm ± 100 cm @ r "rethorl.L (Pe2gi! 221L ¯4 1.i. '%' - - C-4124 15 Turntable nçca (Ïrr1 '\ 1estic [ 1 50 tta- Phny1 75 C-4124 15 Turntable? "Iiisca 00P10C'ti.CF 72" '14tylène - - - Diazinon 20 Turntable r "' é '(': 1 00" "" "'sti ('11 15 Ttra- PhpY1.v1 100 Diazinon 20 Turntable 1 \ T "N '(Ïomr-c: t5 (' ri C6> T) rthy1ene # '- -.- B-31/199 40 Turntable t0urr> R "'t' 1 ifl = P d'1r.r ti-Q2 Té + ra- PhF1 # yl 200 B-21/199 40 Turntable rr, 'lCIl (I (î"' lP :: 1ti.ca 5 Methylene Penta- PI1l1Vl 500 - - Turntable Munca dOTr1 ('1 :: 1ti ("n' methylene - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - .1thYl 'Parathion 10 Turntable "' lc; ca domPti.ca ¯ ¯? 0 P o1- ta-, Ph4nvl 50 Methyl Parathion 10 Turntable, "1Cé'l; or.'1ti (':

  1 flG nethylene # - - C-4l24 15 Turntable, f "('f! NO'": 1. "' <: 1ti.CéJ Fn Penta- Ph4nyrl 75 C-4124 15. Plate turned. N 'us = a (loepUcf GR m0thylne ¯¯¯¯ ¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯ ¯ ¯¯¯¯¯ - - Diazinon 20 P1¯atea.v tourrsrt dnrfl r sti. Ca 1 Po; ta- sethylene Phenyl 100 Diazinon 20 Turntable lI1J.f1ca d0P1Pstic8 8J - - - B-21! 199 40 Turntable 11 Jfusca cloTTI, = stica 38 Penta- Phenyl 200 B-21/199 40 Turntable Husca domestica 52 methylene

  <Desc / Clms Page number 52>

 
 EMI52.1
 hBZAU 15
 EMI52.2
 
 EMI52.3
 Carbamates Phosphate ¯¯¯¯¯¯¯¯¯¯ # ¯¯ 'L Conc.

   Corc. nURntit Powder Po, y'1re (l.;. y "'P" 1 /?; Atbndcn Horta1 té - E- ig 1 10!:! ¯01¯-') cr $ 1 'j' ç 1 Q :: '2 :::.: L - [9E: .¯ ..-: t1; .r1811.G Phenyl 0,5 - -12 a Tour Tet1:' ['ychl1.f1 bi.i'1l'1c1l .1.? Tu8 oyY .. \ thy10ne - - - Melathion o., P5 1.2, E Toiir T0trfl1'1v ('! Hns bim? Cul? Tl1f: f, t1 v hzTene n: vyéthr1ènE =! Phényl 0 , 5 Malathion 0, 5 103 Tour '' r 1 = rl1-xrchus bi.maco7.tr 100 Etl; jrl. Ene, ¯ --- ¯ "" "o: xyÓthylènr> Phényl Q, 5 - - 517 Tour Anasa triptis n -. - -? LaJ-athi.nn n, ù5 oc, 5 Tour Anasa t1: 'i. Pt, i 10 E thyTl. É1? A oxypth; r19ne Ph6nyl 0.5 Malatbion z5 45, 6 Tour A! 1RS3 tri t-ï. [1 ri 1.0n. - ..

      '-..- Tetrp- "' rac'hTr7.pne Phenyl 0.5 - - 55.4 Tour A'a sa. .Ri rf, 3 ;; n - - - a18tnion 0.5 51, 0 Tour Ara sa tr-1.:::ti.s 20 Ttré'1- 1-'1, {t "" YJ)! 10 Pr ntT7, z5 Malathion z5 50, 4 Tour Arara triqti-e 'Tctra-' "" "" "'" ",, r'th, rlne Phenyl C3,5 (, ra1athion - z? Tour 5' m tlor.miécbv s 'hi.iJ1cll1 blS 6 Malathiou z5 5,0 Tour Tf'tT' (1ywchu! '-' h3mac, 't a.fitm 6 Ttram 4 thjrl èn p P1'.nn't7¯ Q ,, 5 iea 1 athi or- 0, 25 5; 0 Turn T! :) t "" ( '!; rcr1U, 8 bi.I1f1.c1l1R.tl.1S 99 p -,: -' "" "- ..¯. ----- .. 11. '..R-' y 't11ylt .;. n0 Phênyï 0,5 - # ¯.¯ 319t¯ T011 !, A1.1aa sad 0 - # - <uaj, ti; j¯; z (l 'ç .: 7 0 "' n 1.," "(i, r :,> j; i, q ra + q¯! 1) (, 1'-1 :. ,, - P11'i: rJ. 0,5 ', Í:; - 11IJt'1Ï'1 "'" I 0. 9.9,7 Turn g, imP g <t., .. i.'Ïtj.r: 90 h. i. i tÏ! .: '1 F' p '",.; = 1,' 1" / '' 1 '' 'rl \' \, ::; - - 4., - "r; 011 ':'" Y -: '1 "rc'18 r \; -' YI, '-' C1.1 '(' t ... fi, r :

   '* '11 ""'. F r '"J') o \ rI '' '' '' ''

  <Desc / Clms Page number 53>

 
 EMI53.1
 Tl: BL "" ln] 1.5 ('1-ï .. t.e)
 EMI53.2
 Carn8rtcs Phosphate ,, z C Reg. Conc. Quantity "r Pou <'1rü Nmfl Powder (Ii y-rps! H,!, +' Hon0 1'f1 ') J "tPt] i té -11- ¯ill¯- ¯ae; cl ¯ n' .2.E :: i S "l :::: t iîT''f '= t7J.

   Ge - - - 1'.1alathion 0, 5 5 Tour Ttra-.nzT,, b..tu 6? Pnt.p-? .Fal thion 0, 25 slour TPtrr.1-jrcf bi.ir = iJ ? <bir xx ^ t?, r¯ene Phnyl 0.5 zlaû; ,, ¯ion C,? 5 5, Tot? r T0t.1 "PY1: rC} 1U kymacolt", 100 ¯¯¯¯¯¯¯¯¯ ¯¯ "JctrrychF bimacnlt

  <Desc / Clms Page number 54>

 EXAMPLE IX. -
Another group of compounds comprising phenyl esters and substituted phenyl esters of N-monosubstituted and N, N-disubstituted carbamates in which one or both oxygen atoms are replaced by sulfur in combination with various derivatives of oxygen is tested. acids containing phosphorus and exercising insecticidal activity. The tests carried out by the turntable method on house flies are described in Table 16.

   The tests carried out by the tower method on Tetranychus bimaculatus are shown in Table 17.-
These combinations also exert a marked synergistic action.

  <Desc / Clms Page number 55>

 
 EMI55.1
 



  TABLF-T-U 16
 EMI55.2
 
 EMI55.3
 C arbBma tes Phosphate 'f ± ¯¯' R5 R6, 3 2 Cone. (agi Con-c. (m.% tôthod deeespi M '!' i: 'Ùi.t' h: .l 117drogen Phenyl 0 8 - 500 - C-4124 15 Pll'te:!. t1 t01U "'1t '!' It l'fusee. DC "'1"' ti.ce C-4l24 15 Plateau tf "tn" n8t'1t usca (1o! '! Pt1.c: o' 1? Tn71 Hydro "'n Phenyl 0 S 75 C-4124. 15 Flat! "8t! Taurrant -: T1! '" CP "o",! "' EH. ('47? HnV':!. H", drone. Phéuyl 'S' S 500 - - - Rotating P1¯ateart ".!" 1tce e. 0- - ti c rPh4 -. D18: z1 ""! On. Ro Plate tO'1! ,,., "'T nt.sQca ro ,. ..ptl 9-7 "Phônyl Hydrog4ne Ph4ndl S 100 Di azi non 20 Plp teau turning i.fnsca domestica 37Ethyl Ethyl Phenyl 500 Plate2n turning ¯? T1.SCP- (! o" 't1ca - - - - - Mt '171 10- Pl1'tN "l t011l" nant? -Iusca do ", ost! Ca t:! 1 Parathion te, *, ti toiir-nant .tusse.



  Ethyl Eth-fl Phenyl S 0 50 tethy1 10 Turntable?! 118. ttortE'st1ca ::: 5. Paathlon -tice -Etlr, 11 Hydrogen 3-? Ethyl- 0 S 500 - - Turntable Musca so! 2tiea ph4nyl - - - C-4124 15 Turntable 'h1see domestica 55 Ethyl Hydrogen .3 3ethyl- 0 a 75 C-4l24 15 Turntable a'usea donestica 49 phenyl.



  Ethyl Hydrogen 3-Yethyl- 0 8 500 Turntable r.rusca (1O! '! T1N!:? H.ny1 - ..... - g299 40 P1.t8.tf!' 8.11 rotating! 1Jc !. dOft! st.1e1! 70 EthY1 Hydrogen 3thyl- 0 S 200 H-23f199 40 # Turntable Musea dOMf! '8ti.ea 50 phenyl If

  <Desc / Clms Page number 56>

   TABLE 17
 EMI56.1
 
 EMI56.2
 
 <tb> Carbamates <SEP> Phosphate
 <tb> Cone. <SEP> Cone. <SEP> Quantity <SEP> mortality
 <tb> @ <SEP> ' <SEP> Powder <SEP> Powder <SEP> (books / <SEP> Method <SEP> in <SEP> @ 4h.
 <tb>
 
 EMI56.3
 



  B - = - RL Il x:!: - X3 .JL Name (%) acre) 9 !!. Su: 't 1 r.:tÎ1Tl Hydrogen Phenyl 0 S 0.5 - - Il, 0 Tower Tptranychus bi!' ICtl1tus 9 - - - - - - Malath10n 0.25, 10.7 Tower Tetranychus bimaculatus 10 Fthjrl Hydrogen Phéntr2 0 S 0, 5 Malathion 0.25 8.9 Tower Tetranychus birt acvi a tus gas Ph ônirl Hydrogen Phenyl SS z 5 -. - 25.2 Tower Tetranychus b1! '1taculp. tTI 4 - - Malathion 0.25 29.5 Tour Tetrenychus bimaculatus 61 Phenyl Hydrogen Phenyl SS 0.5 màlathion 0.25 24.6 Tour Tetranychus Q1mec'1b17 83 Fth; rl Ethyl Ph enyl S 0 0.5 - - 21, 5 Tour Te tranjrchu s b1macHltus 1 - - - - - Malathion 0.35 28.7 Tour 'Tetranychus! b1Y! 'actütns' 6 T'thy1 Ethyl Phenyl S 0 0.5 Malathion 0.25 17.4 Tour Tetranychus b1rnacul. "h1s 100' E'thyl Hydrogen 5-Methyl- 0 S 0.5 - - 12, 0 Tower Tetranychus b1me.cnlt1:

  ts 13
 EMI56.4
 
 <tb> phenyl
 <tb>
 
 EMI56.5
 - - - - Malathion 0.25 13.0 Tower Tetranychus bimaeulatus 55
 EMI56.6
 
 <tb> Ethyl <SEP> Hydrogen <SEP> 3-Methyl- <SEP> 0 <SEP> S <SEP> 0.5 <SEP> Malathion <SEP> 0.25 <SEP> 10.7 <SEP> Tour <SEP> Tetranychus <SEP> bimaculatus <SEP> 81
 <tb> phenyl
 <tb>
 <tb>
 <tb>
 

  <Desc / Clms Page number 57>

 EXAMPLE X.-
The test results summarized in Table 18 illustrate the existence of a marked synergistic action in a series of ratios between a typical carbamate and a typical insecticide containing phosphorus, following the spray tower method applied to Epilachna varivestis.

  <Desc / Clms Page number 58>

 



    TABLE 18
 EMI58.1
 
 <tb> Carbamates <SEP> .Phosphate
 <tb> Conc. <SEP> Cone. <SEP> Quantity <SEP> Method
 <tb>
 
 EMI58.2
 Powder Powder (lbs / ex¯g1 ± 11.1! ::. L 7To,., Tr.; 'J.



  (cf, L .... Name j ± 1 ¯! 1 ± re) ¯¯ .... ¯.¯.¯ PhÀmirl l..l1pthJrlearbamate 0,1 - - 10 J 2 Tour Epilachna vrri Vf ': : 1ti 0 hrtr7. n¯T ,, Tth.'vlca.rba: mate 0.1 #. - ??, 2 Tower Bpi.Jrcl1na. vr9vstis! '1 P h Àmjrl. N-tethylcarbamate 0.1 - - 76; 6 Tower. l1i.lach'l1 [1 ynri.v '"' f1ti.



  Pl1'Yl '\ rl M-Hthylearbamate 1 - - 10,4 Tour' Prri.lé1chna Vf \ 1: 'i.irr pt.r 20 P'! 1'11 :: JT \ l -: - T0thy1carbemate 1 - - 25.4 Tower E "() i.1Rcl1n VRl" tVf'ti 90 - -?, 1? Lathion 0.1 10.7 Tower Enilaobna varīvrti n - Malathion .0 / L 22 , 7 Tour Epilachna var Ô vr s1; 1 - - Malathion 0, 2 9.1 Tour Epilachna variv0t5R 9 - Malathion 0, 5 8, 3 Tour E! Ji1achna variventip 5
 EMI58.3
 
 <tb> - <SEP> - <SEP> Malathion <SEP> 0.5 <SEP> 17.9 <SEP> Tour <SEP> Epilachna <SEP> varivestis <SEP> 25
 <tb> - <SEP> Malathion <SEP> 0.5 <SEP> 25.9 <SEP> Tour <SEP> Enilachna <SEP> varivestis <SEP> 55
 <tb>
 
 EMI58.4
 P h 6mjrl IV-Methylcarbamate 1 Malathion 0.1 17., 3 Round Epilachna varivestis 75 Phenyl N-Methy1carbamate 1 Malathion 0.1, 23.8 Round Epilachna varivfistis 100
 EMI58.5
 
 <tb> Phenyl <SEP> N-Methylcarbamate <SEP> 1 <SEP> Malathion <SEP> 0.2 <SEP> 9,

  1 <SEP> Tour <SEP> Epilachna <SEP> varivestis <SEP> J <SEP> 0 <SEP> 0 <SEP>
 <tb> Phenyl <SEP> N-Methylcarbamate <SEP> 0.1 <SEP> Malathion <SEP> 0.5 <SEP> 7.0 <SEP> Tour <SEP> Epilachna <SEP> varivestis <SEP> 57
 <tb>
 
 EMI58.6
 Phenyl N-1 <Eethylcarbamate 0.1 Malathion 0.5 14.4 Tour 'Epilachna varivestis 100 Phenyl N-Methylcarbamate 0.1 Malathion 0, 5 21.1 Tour Epilachna varivestis 100'

  <Desc / Clms Page number 59>

 
Although particular forms of the present invention have been described above, it will be understood that the invention is not limited thereto and that various modifications can be made thereto, without departing from its scope.



   CLAIMS
1.- Insecticidal composition, characterized in that it comprises a synergistic combination of an organic compound containing phosphorus and an organic carbamate.



   2. Insecticidal composition, characterized in that it comprises a synergistic combination of an organic derivative of an acid containing phosphorus and an organic oarbamate.



   3.- Insecticidal composition, characterized in that it comprises a synergistic combination of an organic phosphate and an organic carbamate.



     4.- Insecticidal composition, characterized in that it comprises a synergistic combination of an organic thiophosphate and an organic carbamate.



   5.- Insecticidal composition, characterized in that it comprises a synergistic combination of an organic compound containing phosphorus and an aryl ester of carbamic acid.



   6.- Insecticidal composition, characterized in that it comprises a synergistic combination of an organic compound containing phosphorus and an aryl ester of an N-monosubstituted carbamic acid.



   7. Insecticidal composition, characterized in that it comprises a synergistic combination of an organic compound containing phosphorus and of a substituted aryl ester of an N-monosubstituted carbamic acid.



     8.- Insecticidal composition, characterized in that it comprises a synergistic combination of an organic compound containing phosphorus and an alkyl ester of an N-monosubstituted carbamic acid.



   9.- Insecticidal composition, characterized in that it comprises a synergistic combination of an organic compound containing phosphorus and a substituted alkyl ester of an N-monosubstituted carbamic acid.



   10.- Insecticidal composition, characterized in that it comprises a synergistic combination of an organic compound containing phosphorus and an alkenyl ester of an N-monosubstituted carbamic acid.



   11. Insecticidal composition, characterized in that it comprises a synergistic combination of an organic compound containing phosphorus and an aryl ester of an N, N-disubstituted carbamic acid.



     12. Insecticidal composition, characterized in that it comprises a synergistic combination of an organic compound containing phosphorus and a substituted aryl ester of an N, N-disubstituted carbamic acid.



   13.- Insecticidal composition, characterized in that it comprises a synergistic combination of an organic compound containing phosphorus
 EMI59.1
 and an alkyl ester of a substituted NId.i. carbamic acid.



   14.- Insecticidal composition, characterized in that it comprises a synergistic combination of an organic compound containing phosphorus and a substituted alkyl ester of an N, N -disubstituted carbamic acid.

** ATTENTION ** end of DESC field can contain start of CLMS **.


    

Claims (1)

15.- Insecticidal composition, characterized in that it comprises <Desc / Clms Page number 60> a synergistic combination of an organic compound containing phosphorus and an alkenyl ester of an N, N-disubstituted carbamic acid. 16.- Insecticidal composition, characterized in that it comprises a synergistic combination of an organic compound containing phosphorus and an organic thiocarbamate. 17.- Insecticidal composition, characterized in that it comprises a synergistic combination of an organic compound containing phosphorus and an organic dithiocarbamate. 18. Synergistic insecticidal composition, characterized in that it comprises an organic compound containing phosphorus chosen from the group formed by the compounds represented by the structural formula: EMI60.1 where X is selected from the group consisting of oxygen and sulfur; R1 and R2 are chosen from the group formed by the alkoxy and dialkylamino radicals; and R3 is selected from the group formed by alkyl, substituted alkyl, aryl, substituted aryl and heterocyclic radicals and radicals represented by structural formula 1 EMI60.2 where R1and R2 and X are as defined above; and an organic carbamate. 19.- Synergistic insecticidal composition ,. characterized in that it comprises an organic compound containing phosphorus selected from the group formed by the compounds represented by the structural formula: EMI60.3 where X is selected from the group consisting of oxygen and sulfur; R1 and R2 are chosen from the group formed by alkoxy and dialkylamino radicals; and R3 is selected from the group consisting of alkyl, substituted alkyl, aryl, substituted aryl, heterocyclic, thiophosphates and phosphates radicals, and an organic carbamate having at least one hydrogen atom attached to the nitrogen atom. 20.- Synergistic insecticidal composition, characterized in that it comprises an organic compound containing phosphorus selected from the group formed by the compounds represented by the structural formula. EMI60.4 <Desc / Clms Page number 61> where X is selected from the group consisting of oxygen and sulfur; R1 and R2 are selected from the group formed by the alkoxy and dialkylamino radicals; and R is selected from the group consisting of alkyl, substituted alkyl, aryl, substituted aryl, heterocyl, thiophosphate and phosphates and an organic carbamate having a monosubstituted nitrogen atom. 21.- Synergistic insecticidal composition, characterized in that they comprise an organic compound containing phosphorus selected from the group formed by the compounds represented by the structural formula EMI61.1 where X is selected from the group consisting of oxygen and sulfur; R1 and R2 are chosen from the group formed by alkoxy and dialkylamino radicals; and R3 is selected from the group consisting of alkyl, substituted alkyl, aryl, substituted aryl, heterocyclic, thiophosphates and phosphates *% radicals, and an organic carbamate having a disubstituted nitrogen atom. 22.- Insecticidal composition, characterized in that it comprises an organic derivative of a compound containing phosphorus and an organic carbamate in an inert insecticidal adjuvant serving as a vehicle. 23. A process for improving the ability of an insecticidal composition comprising an organic compound containing phosphorus to kill and kill insects, characterized in that this composition is combined with an organic carbamate. 24.- A method of improving the ability of an insecticidal composition comprising an organic carbamate to kill and kill insects, characterized in that there is combined with this composition an organic compound containing phosphorus. 25. An improved method for destroying insects, characterized in that the insects are contacted with a synergistic combination of an organic compound containing phosphorus and an organic carbamate. 26. The invention described above in all its novel and useful aspects.