BE552284A - - Google Patents

Description

       

   <Desc / Clms Page number 1>
 
 EMI1.1
 



  The present invention () ()) W;: elYH: 1 T'.r,: ßia (i74ô.n 1 new wtJ'tEl7 '(; $' C.'e organized from the Gx'ï: 'ï! 21 (j; gdl'1Ó: t'ale
 EMI1.2
 
 EMI1.3
 i: .i'z: which R R-1 R and t4 H4 represent 3.coyliqu3S residues, c: yt :: l (jal (: on ", i'i.1mtr ;! C, s' ..t3i 'appliques o; .H; Ól'oy1: 1qu0: in4 ,! a P¯;.: yS'à'ô 5r.bf:rUt\\,:h3, Bzz d:

   R7 9 dci2iie

 <Desc / Clms Page number 2>

 on the one hand, and R3 and R4, on the other hand, which can also be members of a cyclic system, R3 and R4 can moreover also represent hydrogen, R2 represents hydrogen, an alkyl residue or an atom halogen, R5 represents the remains
 EMI2.1
 (R6 denotes an alcoholic, arlic or heterocyclic residue), X and Y represent -0-, -S-, -NH- or -NR-, and Z represents oxygen or sulfur, and n and m are numbers integers with a value at most equal to 2;

   or compounds of formula, general
 EMI2.2
 in which R, R1, R2, R3, R4, R6, X, Y, Z and n and m have the meaning given above. Until now, it has not yet been possible to determine with certainty which of formulas (I) or (II) should be attributed to the compounds. in accordance with the invention. It is possible that, depending on the procedure, only one form or the other is formed, or that one form arises in preference to the other.

   he

 <Desc / Clms Page number 3>

 is known that by reacting? according to Michaelis and Arbuzow of the trialkyl units on certain halogen compounds it produces transpositions so that instead of the expected phosphonic acid esters isomeric esters of phosphoric acid are formed.

   In the case of the invention, the condensation product of [alpha], [alpha] -dichloroacetylacetic acid diethylamide and of trimethyl phosphite can, for example, correspond to the following two types of formulas:
 EMI3.1
 
The present invention therefore embraces the compounds of formulas (I) and (II), as well as their possible mixtures, since the isomerism of the compounds can be interpreted as a keto-enol tautomerism. When, in co which will follow, one will indicate only one form, it will always be necessary to consider also the other form, insofar as it seems able to exist.



   These new compounds are valuable agents in the fight against harmful organisms, especially against

 <Desc / Clms Page number 4>

 harmful organisms belonging to the animal kingdom. They act on the different stages of development of these organisms, for example on the eggs, the larvae, the imagos, and one envisages an action by contact and by ingestion. Suitable substituted compounds exhibit, when used for plants, an internal, so-called systemic, therapeutic action.

   Of particular value are the compounds of the general formula
 EMI4.1
 in which R and R .. represent low molecular weight alkyl radicals comprising from 1 to 4 carbon atoms, and R3 and R4 represent hydrogen or also low molecular weight alkyl radicals comprising from 1 to 4 carbon atoms .



   The compounds in accordance with the invention can be obtained by condensation of a compound of formula
 EMI4.2
 where R, R1, n, m, X, Y and; Z have the meaning given above, and R7 represents a low molecular weight alkyl residue having 1 to 4 carbon atoms, with

 <Desc / Clms Page number 5>

 a compound of formula
 EMI5.1
 in which R2, R3, R and R5 have the meaning given above, and Hal represents a halogen atom, such as bromine or, preferably, chlorine, with elimination of a compound R7-Hal.



   These new products can also be obtained by reacting a compound of formula
 EMI5.2
 in which R, R1, n, m, X, Y and Z have the meaning given above and where Me represents an alkali metal, preferably sodium, on a compound of formula
 EMI5.3
 in which R2, R3, R4, R5 and Hal have the meaning given above. To prepare compounds in which R 2 represents hydrogen or an alkyl residue, the following condensation can also be carried out?
 EMI5.4
 

 <Desc / Clms Page number 6>

 The accessibility of the starting materials determines the choice of the reaction.



   Compounds of the general formula
 EMI6.1
 which are usable as starting materials are derived from trivalent phosphorus, while the products used according to the invention are derivatives of pentavalent phosphorus.



   Among the compounds of the formula which has just been indicated, those in which the symbols X, Y and Z represent oxygen are the most easily accessible. They meet the general formula
 EMI6.2
 and can be prepared according to known methods.



   If R and R1 represent aliphatic radicals, these can be straight chain or branched, saturated or unsaturated; moreover, they can be substituted or unsubstituted. Mention will be made, for example, of the following groups methyl, ethyl, propyl, isopropyl, butyl, hexyl, '
 EMI6.3
 2-ethylbutyl, oc'tyl, 2-butyloctylt, lauryl, octadcyl, allyl, 2-chlorethyl radicals comprising CNS groups, ON or ester groups. The remainders R and R, can

 <Desc / Clms Page number 7>

 
 EMI7.1
 be identical or ditf: rent (3. r.t1 S8t preferably an alkyl y'sste, iqu0 of low weight moXéc: ïÛaiY \ 'J3 comprising from 1 to 4 carbon abomss.

   The following compounds, for example, may be mentioned: triethyl phosphite, triethyl phosphite, tripropyl phosphite, diethyl phosphite, methyl phosphite, tri (2-chlorethyl) phosphite or ester. in formula
 EMI7.2
 
 EMI7.3
 IF R and RI represent aromatic radicals, they can be mono or polynuclei and can still, the
 EMI7.4
 optionally, the ring substituents; we will quote the
 EMI7.5
 phenyl, 2 or 4-chlorophenyl, 24-dishloyophenyl, - "# methoxyphenyl, 4-nltrophenyl naphthyl, or 4-biphenyl.



  Such compounds are contemplated such as 2,-dlehloropienyl-ethylphosphite or 4-chlorophenyl-dimethyl phosphite. In addition, the compounds should be indicated in
 EMI7.6
 which one or two residues are directly linked by an atom
 EMI7.7
 carbon to 1 atom phcsphos'aj, for example diethyl phenylphosphinate of the formula
 EMI7.8
 
 EMI7.9
 If R and E1 represent ara11phatlues radicals, we

 <Desc / Clms Page number 8>

 will cite the benzyl residue; if they represent cyoloaliphatic radicals, the cyclohexyl residue will be mentioned and if they represent heterocyclic radicals, the tetrahydrofurfuryl residue may be mentioned.

   Starting materials having such residues are, for example, cyclohexyl-diethyl phosphite, tetrahydrofurfuryl-dimethyl phosphite, or dibenzylpropyl phosphite. Among the compounds in which X and Y represent sulfur, mention will be made of triethyl thiophosphite, of formula
 EMI8.1
 and among those in which X and Y represent nitrogen, the compound of formula
 EMI8.2
 Compounds of general formula
 EMI8.3
 are salts of disubstituted phosphites or of phosphinic acids, such as, for example, the sodium salts of dimethyl phosphite, of diethyl phosphite, of lauryl-ethyl phosphite, of cyclohexylmethyl phosphite,

   tetrahydrofurfurylethyl phosphite or benzylethyl phosphite.



   Compounds of the general formula

 <Desc / Clms Page number 9>

 
 EMI9.1
 
 EMI9.2
 are monohalides of phosphoric acids, such as, for example, diethyl phosphate monochloride, diethyl thiophosphate monochloride or bis-dimethylamidophosphoric acid monochloride.



   Compounds of the general formula
 EMI9.3
 are amides of halogenated acylacetic acids, preferably acetylacetic, cyanacetic, and malonic acids. The R3 and R4 residues can have the meanings given above for the R and R1 residues. They preferably represent low molecular weight alkyl groups comprising from 1 to 4 carbon atoms, or they form the members of a heterocyclic ring, for example morpholine, piperidine, or aniline.



   The residue R2 can represent a halogen atom, preferably a chlorine atom, a hydrogen atom or a
 EMI9.4
 alkyl residue, preferably comprising from 1 to 4 carbon atoms, such as methyl residue. As already indicated above, the residue R5 can represent a -CO-Rg or -COORg residue. The R6 radical can represent a heterocyclic residue, an aryl residue, for example restēphenyle, chlorophenyl,

 <Desc / Clms Page number 10>

   nitrophenyl or, in particular, an alkyl residue comprising from 1 to 4 carbon atoms.

   The residue R6 is preferably a methyl group and the residue R5 a -COCH3 group, that is to say the. starting compounds are, de..préférence.
 EMI10.1
 amides of 11 aldeacety) a: ketic, Panai; the reaction components of the formula mentioned in the last place include: dichloroacetylacetic acid dîethylamide, dl-bromocyanacetic acid amide, monochloract3lctic acid diethylamide or dichloromalonate ethylamide ethyl.



   For the preparation of the products according to the invention, the reaction components a. a certain temperature, for example at 50 - 2000 and, preferably, a temperature of the order of 90 to 150. It may be advantageous or advisable to use together inert solvents such as benzene, toluene, xylene, chlorobenzene or gasoline and, if necessary, to work in an atmosphere of inert gas, for example under a nitrogen atmosphere, and / or under reduced pressure.



   As already indicated at the beginning, the products conforming to the invention constitute valuable agents for the control of harmful organisms. A subject of the present invention is therefore also, on the one hand, preparations for combating harmful organisms containing as active substances the products in accordance with the invention and²

 <Desc / Clms Page number 11>

 on the other hand, a method for controlling, using such preparations, harmful organisms.

   Preferably, compounds of the general formula are used
 EMI11.1
 in which R 1 and R 1 represent low molecular weight alkyl radicals comprising from 1 to 4 carbon atoms, and R 1 and R 4 represent hydrogen or also low molecular weight alkyl radicals comprising 1 to 4 carbon atoms. carbon.



   Bodies which are the most different from each other can be protected from harmful organisms, and for this purpose both gaseous bodies as well as liquids or solids are used as carrier material for the active substances. As a body of this kind to be protected or as a body to be used as a support, it is envisaged, for example, the air, in particular in enclosures, then liquids, such as for example the water of ponds and finally of the dead or living foundations. for example any objects in living rooms, in cellars, in attics, in stables, as well as furs, feathers, wool and the like, as well as organisms of the plant and animal kingdom, in their states of the most varied development,

   as long as they are insensitive to the fighters

 <Desc / Clms Page number 12>

 pests.



   The fight against harmful organisms is carried out in accordance with the invention, according to usual methods, for example by treating the bodies to be protected with the new compounds in vapor form, for example in the form of smoke or in the form of agents. dusting or spraying, for example in the form of solutions or suspensions prepared with water or suitable organic solvents, such as alcohol, petroleum, tar distillates, etc. it is also possible to use aqueous solutions or aqueous emulsions of organic solvents containing the active substances, for brushing, spraying or immersing the objects to be protected.



   The spraying and powdering agents may contain the usual inert fillers or the usual labeling agents, such as, for example, kaolin, plaster or bentonite or other adjuvants, such as sulphite-containing cellulose lye. , cellulose derivatives and the like, as well as customary wetting agents and adhesion agents for increasing wetting power and adhesion. These preparations for controlling harmful organisms can be obtained in powder form, in the form of aqueous dispersions or pastes, or in the form of oils which disperse spontaneously.



   These new compounds can be presented as

 <Desc / Clms Page number 13>

 unique active substance in agents for the control of harmful organisms or also to be present there in mixture with other insecticides and / or fungicides. The use of such preparations for the protection of plants takes place by the usual method of spraying, pouring, dusting and fumigating.



   In the non-limiting examples which follow, the parts are understood by weight. Between each part by weight and each part by volume there is the same ratio as that between the kilogram and the liter. Temperatures are given in degrees centigrade.

 <Desc / Clms Page number 14>

 
 EMI14.1
 mixture, at the L .. ratura ambl & nte, 11 ?? The n ::;:. yt a.Nbljs.ns 11: parts of dichloketylacetyl lithium amide boiling at z5 - 93 under a pressure of 0.18 hkj) and 8 g3 rtie3 of triethyl phosphite are mixed. Afraid make * start '¯ ¯ =: ro: t.cn we heat the mixture to 90. At this point, 1.1 occurs a turbulent gas evolution and the adjusted solution heats up at 1600 without external heat input.

   When the reaction is complete, the product is further concentrated at 950, for a short time, under the vacuum of the water pump.



  There remains a red oil with reflections voi-ts? 16.1 pK "ie ;; which can be purified by distillation so, -, z; 1! 1 vldc pushed. It boils at 14% under a pressure of 0, 1 mm.



  C12H23 5ÎIC1P Calculated: 4.2% 1 IC'SiIIJ 12 - "" 2 '5 Calculated <;, e. bw .... ,, 8 '' - '. Í' '' 'Found N 4.24% Cl 11 The diethylamide of diC1J0tyl01ua acid which is used for the preparation of this pl'cÓ.': lt & .3 oc: d1: 'nt1on can be prepared by chlorsnt A3 d 1 é â. 3 siera acetylacetic using 2 KC'l of '3ulfuryl% chloride <¯Example 3.



  A new Lan 3 3 Sa 3 ?, 8 parts of dlchlcacétylacétiu acid diethylamide and 34 parts of chlorobenzene are heated to the boil. We add to the 5Gtcà-drip,
 EMI14.2
 over 5 minutes 20.5 parts of trimethyl phosphite.



  A violent evolution of gas occurs which is terminated at

 <Desc / Clms Page number 15>

 after one hour of boiling at reflux. The fractions are easily removed under a water pump vacuum; birds and
 EMI15.1
 ehlorobensene, and there is obtained a residue of 5O parts of an orange-tinted oil which can be distilled under a high vacuum. It boils at 138 - 142 under 0.1 mm pressure (37.2 parts 82.6% of theory).



  C10H19O5NClP Calculated: C 40.07% H 6.39% N 4.67% Cl 11.83% P 10.34%
 EMI15.2
 Found C 39.90% H 6 $ 61% N 4; 70 Cl Ile78% P 10.38% Heated to 120.9.6 parts of e! I4ethyl-amMc of monochloroacetylacdtic acid (boiling at 83 - 85 under a pressure of 0.15 mm). 8.3 parts of triethyl phosphite are added dropwise thereto. The temperature of the reaction mixture. tional rises to 155, and ethyl chloride is given off.



  When the dropwise addition is complete, the mixture is further heated at 1500 until the evolution of gas ceases, which is the case within 15 minutes. The last remains of easily volatile fractions are then removed in a water pump vacuum. It naps as a residue 14.0 parts of a light orange tinted oil which is soluble in ether, acetone and alcohol.
 EMI15.3
 



  The diethyl chloride of monochloroacetylacetic acid used herein can be prepared by allowing a mol of
 EMI15.4
 sulfuryl chloride on 11-aefde acetyl- diethylamide

 <Desc / Clms Page number 16>

 acetic.



   Example 4.



   To 9.6 parts of monochloroacetylacetic acid diethylamide which has been heated to 140, 6.2 parts of trimethyl phosphite are added dropwise; there is then a sharp evolution of gas and the temperature rises to 140 - 150. The reaction is terminated at 150 by external addition of heat. After concentrating under vacuum at 95 for a short time, 12.45 parts of a dark red oil remain, which can be purified by distillation under high vacuum.



  It boils at 1430 under a pressure of 0.35 mm.
 EMI16.1
 



  'CloH2005NP Calculated zei 5.28 P Il, 68%
Found: N 5.14% P 11.53% The product is well soluble in acetone and alcohol, and less soluble in ether.



   Example 5.



   Covered with 20 parts by volume of xylene, 8.5 parts of dichloroacetylacetic acid amide (melting point: s 65). The mixture is heated to 90 and 8.3 parts of triethyl phosphite are added thereto dropwise. The temperature is maintained at 110 - 120 without external heating and ethyl chloride evolves from the reaction mixture.



  The solvent is then removed in vacuo at 95. There remains as a residue 13.6 parts of a reddish oil with opalescent green reflections. The product is well soluble in acetone

 <Desc / Clms Page number 17>

 and alcohol- and sparingly soluble in ether.



   Dichloroacetylacetic acid amide can be obtained by chlorinating in chloroform with 2 moles of sulfuryl chloride.



   Example 6.



   To a mixture heated to 90-100 of 8.5 parts of dichloroacetylacetic acid amide and 20 parts by volume of xylene, 6.2 parts of trimethyl phosphite are slowly added so that the temperature is maintained at 110 - 1200 without external heating. When the evolution of gas has ceased, the xylene is removed under a vacuum from the water pump at a bath temperature of 95. The reaction product consists of a reddish oil with green tints (11.5 parts), and it is well soluble in acetone and in alcohol.



     In an analogous manner, it is possible to react with tertiary phosphites the halogenated amides of ss-ketonic acids which are indicated in the table below. The esters formed, the properties of which are also shown in the table, can only be partially distilled under high vacuum and without decomposition. However, for the preparation of the pest control agents, it is unnecessary to purify these compounds by distillation.

 <Desc / Clms Page number 18>

 
 EMI18.1
 
<tb>



  N <SEP> Amide <SEP> of acid <SEP> Amide <SEP> of halogenated <SEP> <SEP> Component <SEP> phosphitic <SEP> and <SEP> properties <SEP> of
<tb> esters <SEP> obtained
<tb>
 
 EMI18.2
 1-2 CH 3 COCIICONHC, 43,. CH, COCC12CONHCH, 0 (CH 3 0) 3 p (C2H50>, P.
 EMI18.3
 
<tb>



  . <SEP> boiling <SEP> has <SEP> 100-102 <SEP> melting point <SEP> <SEP> 59-60 <SEP> oil, <SEP> very <SEP> well <SEP> soluble < SEP> oil, <SEP> soluble <SEP> in
<tb> under <SEP> a <SEP> pressure- <SEP> of <SEP> in <SEP> water, <SEP> 10alcohol, <SEP> water, <SEP> alcohol,
<tb> 0.8 <SEP> mm <SEP> acetone;

   <SEP> boiling <SEP> in <SEP> acetone
<tb> se <SEP> decomposing <SEP> to <SEP> 135
<tb> under <SEP> a <SEP> pressure <SEP> of
<tb> 1.5 <SEP> mm
<tb>
 
 EMI18.4
 3-4 CH, COCH2CONHC2Ha CH 3 cocci 2 CONHO 2 H 5 (CH, 0) -P (C2HSO>, P.
 EMI18.5
 
<tb> boiling <SEP> to <SEP> 120 <SEP> under <SEP> boiling <SEP> to <SEP> 91 <SEP> under <SEP> oil, <SEP> soluble <SEP> in <SEP> oil, <SEP> soluble <SEP> in
<tb> a <SEP> pressure <SEP> of <SEP> 1.8mm <SEP> a <SEP> pressure <SEP> of <SEP> alcohol, <SEP> acetone, <SEP> little <SEP > alcohol, <SEP> acetone *
<tb> 0.15 <SEP> mm <SEP> soluble <SEP> in <SEP> water <SEP> little <SEP> soluble <SEP> in
<tb>
 
 EMI18.6
 5-6 CH, COCH2CONHC, H7 (n) 'CH 3 COCCI 2 CONHO 3 H 7 (n) (CH 3 0) 3 p Îàeguo) ID 9 3 p
 EMI18.7
 
<tb> boiling <SEP> to <SEP> 104-1060 <SEP> oil <SEP> thick <SEP> oil <SEP> thick,

   <SEP> soluble <SEP> oil, <SEP> soluble <SEP> in
<tb> under <SEP> a <SEP> pressure <SEP> of <SEP> in <SEP> alcohol, <SEP> acetone <SEP> alcohol, <SEP> acetone
<tb> 0.4 <SEP> mm; crystallln
<tb>
 
 EMI18.8
 7-8 CH, COCH2CONHC, H1 (iSO) CH, COCC12CONHC, H1 (iSO} (CH, 0) -P (C2HSO), P
 EMI18.9
 
<tb> boiling <SEP> at <SEP> 91-94 <SEP> melting point <SEP> <SEP> 51 <SEP> oil, <SEP> soluble <SEP> in <SEP> oil <SEP> hardly
<tb> under <SEP> a <SEP> pressure <SEP> of <SEP> alcohol, <SEP> acetone <SEP> mobile, <SEP> soluble <SEP> in
<tb> 0.2 <SEP> mm, <SEP> crystalline <SEP> alcohol, <SEP> acetone
<tb>
 

 <Desc / Clms Page number 19>

 
 EMI19.1
 S} .. m1de of acid 1 Jun1de of halogenated acid Component pcapiiu and properties of the esters obtained! 910 CPCOCE2comiCl.H9 (n) 0 c3CVCCaaarHC, x9'n (cif3o 3p c == 5cx.

   boiling at 110-114 thick oil oil, soluble in thick oil, soluble under a pe5 $ 1on of alcohol, acetone in l! alcoolaceO2 mm, crystalline alcohol, 1 acetone tone alcohol, ae- j w1-12, CH¯COCH2CONfC) 2 CH-COCHCICON (CH-) 2 (CH 0) (C HO) ..? boiling! J. 75-7i '> boiling at 95 in mobile oil, soluble in 1 oil;

   solub26 in under a passion of pressure, 0.7 mm in alcohol, 8, .-. coo 8 = b W ^ 1Z.3-14 f 1,8 Er HIJOCC1CON <C: H- = :) tons (C2HhOYJ? rOC1 u9hI II (Clî- 0 j 3 5 ::; J .... boiling 8 7Ô in oil, soluble in! oil. boil 1.11e.t at 1 a pressure of 0.035 alcohol, acetone! 152-156 under a ram 1 pressure of 0235 l! 1 ... 'nJ' (w: stJ. ".iPw 'alecol 15a.cetor3! S p5% .ß, 3â:, ZH! G' '. 2f. 0., H, [{CH3} 2CH01:; p!' boiling at, 5-7o boiling to 92.5-93 oil fluiÓe3 solbl under a pressure of under a pressure of in alcohol, 1 DC-I 0.58 mm 0.18 mm tone î26 "17! 2 CON (C 2H 5) 2 (CBjO) 3? CS2Hr0) ¯F '2.5-17 f boiling at 88-89.5 oil, soluble in oil,, NS'7,' âa da * under a pressure of water, alcohol, 1 l "e. au., É. -4? ô bzz acetone!!]. acé ":

  or0 "" 'I # ""

 <Desc / Clms Page number 20>

 
 EMI20.1
 
<tb> N <SEP> Amide <SEP> of acid <SEP> Amide <SEP> of halogenated <SEP> <SEP> Component <SEP> phosphitic <SEP> and <SEP> properties <SEP> of
<tb>
 
 EMI20.2
 ###, .¯.¯¯¯¯¯¯¯¯¯¯¯¯ ¯¯¯¯¯¯¯¯¯¯¯¯¯ '' esters obtained 18-19 C'8, COOH200N (O, H7n) 2 CH300OC12CON (C 3H 7n) 2 (CH30) 3P.

   (C2HSO) JP. bPU1114 ta 83 "84 boiling at 94-1020 oil, soluble in oil readily under alcohol pressure, mobile acetone, soluble in 20-21 .0.52 mm. ut mm CON ( C% H7180) 2 - alcohol, acetone 20-21 3 7100) 2 CH, COCC12CON (C, H7iSO) 2 (CH 3 0 3 P (C2H50), P boiling at 87-90 melting point 60 oil, boiling to yellowish oil, soluble under a.

   pressure of 1540 under a pres- in alcohol, ltaa- '7 mmo sion of 0.35 mm, sotone
 EMI20.3
 
<tb> fad <SEP> in <SEP> alcohol,
<tb> acetone <SEP> ¯ <SEP>
<tb>
 
 EMI20.4
 22-2 'CH, COOH2CON (C4H9> a Ca, COCC12CON (C4H9n) 2 (OH30) 3p ------ CC2H50)} P boiling at 102- boiling at 134 - oil, soluble in oil, soluble in
 EMI20.5
 
<tb> 1040 <SEP> under <SEP> a <SEP> 1360 <SEP> under <SEP> a <SEP> under <SEP> alcohol, <SEP> acetone <SEP> alcohol, < SEP> acetone <SEP>
<tb> pressure <SEP> of <SEP> 0.63 <SEP> mm <SEP> pressure <SEP> of <SEP> 0.25 <SEP> mm
<tb>
 
 EMI20.6
 24 Cfl) COCH200NHH2 OH, COCC1CONH "2 (CH 0) P a, COCH2CONHCH2 CI3COCCl, CONHCH, oil, hardly melting point 165- melting point 970 mobile, soluble in 1660 i'uaion i65.- usion 97o alcohol, acetone 25..26 CB, OOCH2corm - (! D CH, COCC12CONH- <IC> (CH 3 0 3 P (CH-0)

   P melting point oil Yellow, soluble thick oil, soluble
 EMI20.7
 
<tb> 71.5 @ <SEP> - <SEP> 72 <SEP> 54 <SEP> - <SEP> 560 <SEP> in <SEP> alcohol, <SEP> ac- <SEP> in < SEP> alcohol, <SEP> acetone <SEP> tone
<tb>
<tb>
 

 <Desc / Clms Page number 21>

 
 EMI21.1
 NO Diacid amide Halogenated acid amide Phosphitic compound and properties of
 EMI21.2
 
<tb> esters <SEP> obtained
<tb>
 
 EMI21.3
 27-28 CH3coCH2cOim-s: ü => CH, COCC2COl'm-W (CH30P,. "" 'I (' C21'O .; 'CH point CHL point oil, soluble in oil. Soluble in melt. 'C3 ^ lp' fusion 56-57 'alcohol, acetone alcohol, acetone' 29-30 ck3CQCH2CO-S ± 2> # 'CH; SCOCC12èO-l't = - ..>.

   (CH30) 3 (C2H5Q} 3P 'boiling to boiling at 122 under oil, soluble in oil soluble in ii 107 under a pressure of 0.55 rom 3'a.at, .aan j alcohol, acetone c pressure of 1 mm ....! 31-32 icH-, COCCO - "" 0 caâ, coc ca - .. ¯, o CCIUOP {CH50-P melting point thick oil thick oil, yellow oil soluble in 65 - 67 'clear soluble in ethers Palcool1J alcohol, acetono, acetoiae 30 CH3coCH "COIrn--:

   CH7, COCC12COI1-7. ':'. , Alcohol,. oacetone! 1 Pacêto: ae (C ", H ... O} P melting point 85 'melting point 47 1 ::> thick ab
 EMI21.4
 
<tb> the <SEP> in <SEP> alcohol, <SEP>
<tb> 1 * <SEP> acetone <SEP>
<tb>
 
 EMI21.5
 z-35 CH-.COCHCOM'-Cl Cl'I3coC12Cmm {:), Cl cn ;; O) 3P (eH,: 0)) P melting point melting point 55-56 thick oil, soluble \ thick oil, solnb - 124 in alcohol:, 9 acele in alcohol ;, "1" tone to 1U 8.etcme, 1 C eth @ X '..

 <Desc / Clms Page number 22>

 
 EMI22.1
 



  No. - Acid Amide Halogenated Acid Amide Phosphetic component and properties of the esters obtained 36-37 ccoc2oz-r ''. CH, O? OC12CONH- <(CH30) 3 p. ' (C2H50) 3P
 EMI22.2
 
<tb> point <SEP> of <SEP> fu- <SEP> Ç ': 1 <SEP> and <SEP> boiling <SEP> to <SEP> Cl <SEP> Cl <SEP>. <SEP> viscous <SEP> oil, <SEP> solub- <SEP> viscous <SEP> oil,
<tb>
 
 EMI22.3
 sion $$ - 890 124-1260 under a pressure in alcohol, soluble in the alsion of 0.05 mm acetone cool, acetone 38-39 c7coCteQC252o cH.cocc2cou (cHS (c3o (C2HSO> 3P Boiling at 101-1020 easily mobile oil soluble mobile oil mobile oil, soluble
 EMI22.4
 
<tb> under <SEP> a <SEP> pressure <SEP> of <SEP> in <SEP> alcohol, <SEP> ac- <SEP> in <SEP> alcohol,
<tb> 0.2 <SEP> mm <SEP> tone <SEP> acetone
<tb>
 
 EMI22.5
 1 f -COCH2CON (C2HS> 2 2 2 5) 2 fluid oil, soluble fluid oil,

   thick solubhulle in alcohol, Itaceous in alcohol, boiling at 112 us thick oil tone 1> alC o1 'llaceous- acetone
 EMI22.6
 
<tb> a <SEP> pressure <SEP> of <SEP> aefcone
<tb> 0.15 <SEP> mm
<tb>
 
 EMI22.7
 42-43) ¯ ,, ooCco (c5y2 .cooClcorQC2 (CH30) 3p (C2HSO), P, boiling% a 134-1350 melting point 55-560 thick oil, soluble thick oil, soluble
 EMI22.8
 
<tb> under <SEP> a <SEP> pressure <SEP> of <SEP> point <SEP> of <SEP> merge <SEP> 55-56 <SEP> in <SEP> alcohol, <SEP> the ac- <SEP> in <SEP> alcohol, <SEP> ac-
<tb> 0.1 <SEP> mm <SEP> tone <SEP> tone
<tb>
 

 <Desc / Clms Page number 23>

 
Example 7
The mixture is heated to 130.12.8 parts of ethyl dichloromalonate diethylamide (boiling to 88 under a pressure of 0.04 mm).

   By slowly adding 8.3 parts of triethyl phosphite dropwise, the temperature automatically rises to 165. When the dropwise addition is complete, the reaction mixture is further heated for a short time until the evolution of gas ceases, and then it is concentrated in vacuo. There remains as residue 17.7 parts of a red oil which is well soluble in ether, acetone and alcohol (the theoretical yield is 17.9 * parts).



   The ethyl dichloromalonate diethylamide which is used here can be prepared from the non-chlorinated compound, using 2 moles of sulfuryl chloride.



   Example 8
 EMI23.1
 6.2 parts of trimethyl phite are added dropwise to 12.8 parts of ethyl dichloromalonate diethylamide previously heated to 130 in an oil bath. A strong current of methyl chloride is released and the temperature of the mixture rises to 155. The reaction is terminated by heating briefly. The last remaining volatile fractions are then removed under a water pump vacuum. The reaction product consists of a reddish brown oil (16.4 parts) which is not well soluble.

 <Desc / Clms Page number 24>

 in ether / maize is well soluble in acetone and alcohol.



   Example 9
12.1 parts of dibromocyanacetamide (melting point: 126) are mixed with 20 parts by volume of absolute benzene, then heated to 60. 8.3 parts of triethyl phosphite are added dropwise so that the reaction temperature is maintained at 60-80 without addition of heat. The dibromocyanacetamide then goes completely into solution and ethyl bromide is evolved. The benzene is then evaporated off under vacuum. There remains 15.1 parts of dark red oil which is easily soluble in acetone and alcohol, but hardly soluble in ether.



   Example 10
A mixture of 12.1 parts of dibromocyanacetamide and 20 parts by volume of absolute benzene is heated to 60 and 6.2 parts of trimethyl phosphite are added dropwise thereto. When the rapid evolution of gas ends, the solvent is evaporated off in vacuo.

   A dark red oil (13.9 parts) remains as the reaction product, which readily dissolves in acetone and alcohol.

 <Desc / Clms Page number 25>

 
Example 11 In 15 parts by volume of xylene, the mixture is heated
 EMI25.1
 to Itébul11tipn, 11.3 parts of d.hylam3.de of dichloroacetylacetic acid and add to the mixture, during 5 minutes, 12.2 parts of phosphite of diethyltetrahydrofur-
 EMI25.2
 furyl of formula (C25t2i-OGi3, r (boiling at 59 under a pressure of 0.4 mm). To terminate the reaction, the mixture is kept for one hour at the boiling temperature. 5 parts of ethyl chloride.

   The xylene is removed under ordinary vacuum, then, small amounts of starting material still present are removed under high vacuum, at a bath temperature of 100-190.



  There remains as a residue 14.9 parts of a clear oil which dissolves very well in acetone and alcohol, but which dissolves less well in water.



   In an analogous manner, the following phosphites are reacted with dichloroacetylacetic acid diethylamide.

 <Desc / Clms Page number 26>

 
 EMI26.1
 
<tb>



  Phosphite <SEP> Product <SEP> resulting <SEP> of <SEP> the <SEP> reaction <SEP> of <SEP> phosphite <SEP> and <SEP> of
<tb> diethylamide <SEP> from <SEP> dichloroacetylacetic acid <SEP>
<tb>
 
 EMI26.2
 
<tb> (C2H5O) 2P-OCH2CH = CH2 <SEP> Clear oil <SEP>, <SEP> soluble <SEP> in <SEP> alcohol <SEP> and <SEP> acetone
<tb> boiling <SEP> to <SEP> 64-66 <SEP> under <SEP> a
<tb> pressure <SEP> of <SEP> 12 <SEP> mm <SEP>
<tb> (C2H5O) 2P-OC2H4SC2H5 <SEP> Oil <SEP> thick, <SEP> soluble <SEP> in <SEP> alcohol <SEP> and <SEP> acetone
<tb> boiling <SEP> to <SEP> 59-61 <SEP> under <SEP> a
<tb> pressure <SEP> of <SEP> 0.1 <SEP> mm
<tb> (C2H5O) 2P-OCH2 <SEP> # <SEP> Oil, <SEP> soluble <SEP> in <SEP> alcohol <SEP> and <SEP> acetone
<tb> boiling <SEP> to <SEP> 84 <SEP> under <SEP> a
<tb> pressure <SEP> of 0.3 <SEP> mm
<tb> (C2H5O)

  2P-O <SEP> # H # <SEP> Easily mobile <SEP> oil <SEP>, <SEP> soluble <SEP> in <SEP> alcohol,
<tb> acetone
<tb> boiling <SEP> to <SEP> 50 <SEP> under <SEP> a
<tb> pressure <SEP> of <SEP> 0.3 <SEP> mm <SEP>
<tb> (C2H5O) 2-P-O <SEP> #Cl <SEP> Oil <SEP> thick, <SEP> soluble <SEP> in <SEP> alcohol, <SEP> acetone
<tb> 5 <SEP> # <SEP> Thick oil <SEP>, <SEP> soluble <SEP> in <SEP> alcohol, <SEP> acetone
<tb> boiling <SEP> to <SEP> 70-75 <SEP> under
<tb> a <SEP> pressure <SEP> of <SEP> 0.1 <SEP> mm
<tb>
 

 <Desc / Clms Page number 27>

 
Example 12
Heated to 1500, 11.3 parts of dichloroacetylacetic acid diethylamide and added dropwise over the course of 5 minutes, 7,

  5 parts of ethyl phosphite
 EMI27.1
 ethylene of formula 'C250 C¯C2 (boiling at 49 under H2 at a pressure of 10 mm). The mixture is still maintained for an hour and a quarter at 160, so that the evolution of ethyl chloride has ceased. 1.2 part of ethyl chloride is collected. The reaction does not proceed in a unitary fashion with elimination of ethyl chloride, but also proceeds partially by itself with cleavage of the ethylene phosphite ring. The starting materials still present are removed under a high vacuum at a bath temperature of 1800 and a viscous oil (10.8 parts) is obtained as a residue which is well soluble in alcohol and acetone, but is less well soluble in water.



   Example 13 11.3 parts of dichloroacetylacetic acid diethylamide are heated to 180. It is added dropwise over 5 minutes, Il, 7 will start from trithioethyl phosphite and the evolution of ethyl chloride is allowed to decrease for 1/4 hour at 180. The starting materials present are removed under a vacuum at 150 and obtained as

 <Desc / Clms Page number 28>

 Residue a viscous mass (17.6 parts) which is readily soluble in chloroform, but less soluble in alcohol and acetone.



   Example II At boiling point, 10.6 parts of N-diethyl-amidophosphite are added over the course of 5 minutes.
 EMI28.1
 0-diethyl of formula (C2H50) 2PN (C2HS) 2 to a mixture of 11.3 parts of dichloroacetylacetic acid diethylamide and 15 parts by volume of xylene. After 10 minutes the evolution of ethyl chloride (3.0 parts) is complete.



  The xylene is removed under a water pump vacuum and then the small amounts of the starting material still present are removed under a high vacuum at a bath temperature of 180. A clear, easily mobile oil is obtained as residue, which is well soluble in alcohol and acetone, but which is sparingly soluble in water.



   Example 15
3 parts of dichloroacetylacetic acid thylamide are heated to the boiling point with 15 parts by volume of xylene and 10.9 parts are added dropwise thereto.
 EMI28.2
 diethyl phenylphosphonite formula / T \ / of d1ethyl PhenylPhOBPho1te of formula: :( Oa2H5) 2
 EMI28.3
 (boiling at 10d-114- under 10mm pressure). The reaction is. completed in an hour and we can collect

 <Desc / Clms Page number 29>

 2.8 parts of ethyl chloride. After removing the xylene under normal vacuum and then removing the small amounts of starting material still present under high vacuum, at a bath temperature of 180, 15.4 parts of a thick oil are obtained which is well soluble in water. alcohol and acetone.



   Example 16
13.8 parts of diethyl phosphite are added dropwise to a suspension of 2.3 parts of sodium chips in 70 parts by volume of ether. As soon as all the sodium is in solution, a mixture of 20.6 parts of α-chloro- [alpha] -methylacetylacetic acid diethylamide (boiling at 87 under a pressure of 87) is added dropwise at 20-30. 0.15 mm) and 30 parts by volume of ether. The mixture is heated for another six hours at the boiling point under reflux and, after cooling, the sodium chloride is washed with little water. The ethereal solution was dried over sodium sulfate, the ether was distilled off and the residue (22.6 parts) distilled under high vacuum. This gives 13.7 parts of a yellowish oil which boils at 141-148 under a pressure of 0.15 mm.



  Calculated C13H26O5NP; N 4.56% P 10.08% found: N 4.49% P 10.13%
In a similar way, the salt is reacted

 <Desc / Clms Page number 30>

 sodium hydroxide of diethyl phosphite with α-chloroacetylacetic acid diethylamide and a compound of the crude formula C12H24O5NP boiling at 1320 under a pressure of 0.2 mm is obtained.



  Calculated C 49.14% H 8.25% N 4.78% P 10.56% Found: C 49.26% H 8.30% N 4.82% P 10.52%.



   Similarly, the sodium salt of dimethyl thiophosphite can also be reacted with α-chloroacetylacetic acid diethylamide.



   Example .17
To a suspension of 2.3 parts of sodium chips in 200 parts by volume of dioxane is added dropwise to 50-60 17.3 parts of acetylacetic acid diethylamide. The sodium goes into solution within 2 hours, causing the evolution of hydrogen. The solution of the sodium salt is cooled to 35 and, with stirring, 18.9 parts of diethyl thiophosphate chloride are added dropwise. The solution is further stirred for 1 1/2 hours at 45 minutes. At the end of this time, the separation of the sodium chloride is complete. The mixture is filtered and the solvent is removed by distillation under a water pump vacuum.

   32.4 parts of an easily mobile oil remain which readily dissolves in alcohol and acetone and cannot be distillable under high vacuum.

 <Desc / Clms Page number 31>

 



   Similarly, the sodium salt of α-methylacetylacetic acid diethylamide (boiling at 870 under 0.08 mm pressure) is reacted with diethyl phosphate chloride to give the compound of crude formula C13H26O5NP boiling at 136-1380 under a pressure of 0.1 mm. - Calculated: C 50.80% H 8.53% N 4.56% P 10.08% Found: C 50.64% H 8.39% N 4.59% P 9.97%
Example 18
2.3 parts of sodium chips are added to 800 parts by volume of ether. At the boiling temperature, 15.7 parts of acetylacetic acid diethylamide are added dropwise.

   When all the sodium is dissolved, 17.05 parts of bis-dimethylamidophosphoryl- chloride are added and the reaction mixture is maintained for 4 hours at boiling under reflux. The sodium chloride is then washed with 35 parts by volume of water, the ethereal solution is dried over sodium sulfate and the ether is removed by distillation. There remains as a residue 24.9 parts of a thick oil which cannot be distilled off under high vacuum and which is well soluble in acetone, but slightly less soluble in alcohol and water.

 <Desc / Clms Page number 32>

 



   Example 19
Two parts of the condensation product according to Example 1 or 2 are mixed with one part of the condensation product obtained from one mol of tertiary octylphenol and 8 mol of ethylene oxide, and 7 parts of isopropanol. A clear solution is obtained which can be used as a spray concentrate and which can be emulsified by pouring it into water.



   A. To determine the internal, so-called systemic therapeutic action, the following test was carried out using spray slurries with active substance content of 0.08%, 0.04% and 0.02%.



   Marsh beans (Vicia fabae) which were heavily seeded with leaf aphids (Doralis fabae) were stripped from their lower half and the stem provided with a colored mark at mid-height.



  The lower stem halves of two plants were then sprayed each time with the spray slurries of the concentrations indicated. After 48 hours, the effect on leaf aphids in the unsprayed upper part of the plants was checked. In the table below, the results obtained have been gathered: '

 <Desc / Clms Page number 33>

 
 EMI33.1
 
<tb> Concentration <SEP> of <SEP> the <SEP> slurry <SEP> Effect <SEP> on <SEP> the <SEP> aphids <SEP> in
<tb> to <SEP> spray <SEP> end <SEP> of <SEP> 48 <SEP> hours
<tb>
<tb> Example <SEP> 1 <SEP> Example <SEP> 2
<tb>
<tb>
<tb> 0.08% <SEP> ++ <SEP> ++
<tb>
<tb> 0.04% <SEP> ++ <SEP> ++
<tb>
<tb> 0.02% <SEP> ++
<tb>
 In the table each sign represents a plant;

   + means that there are no more living aphids, {means a good deed, only a few isolated aphids surviving, - means no or insufficient effect.



   B. To determine the contact effect on leaf aphids, the following test was carried out using spray mixtures with active ingredient content of 0.08%, 0.04% and 0 , 02%.



   Marsh bean plants which were heavily seeded by leaf aphids were sprayed on all sides. After 48 hours, the effect exerted was checked. When the effect was 100%, the plants were infected with new aphids and the effect was checked 48 hours later.

   The results are collated in the table below:

 <Desc / Clms Page number 34>

 
 EMI34.1
 
<tb> Concentration <SEP> of <SEP> boiled <SEP> Effect <SEP> on <SEP> <SEP> aphids <SEP> of <SEP> leaves
<tb>
<tb> to <SEP> spray <SEP> At <SEP> end <SEP> of <SEP> 48 <SEP> hours <SEP> after <SEP> the
<tb>
<tb> 48 <SEP> hours <SEP> new <SEP> infection
<tb>
<tb>
<tb> Ex. <SEP> 1 <SEP> Ex. <SEP> 2 <SEP> Ex. <SEP> 1 <SEP> Ex. <SEP> 2
<tb>
 
 EMI34.2
 0.08% 4- + 3 - 'r ++ 4+ {.) 04% -w- ++ ++ +! 0, 2 ++ -H- -H- H C. To determine the effect on aphids by diffusion through the leaves, the following test was carried out using spray slurries exhibiting
 EMI34.3
 an active substance content of 0,, o8y; ,, 0.04% and $ 0.02.



   Marsh beans which only bore leaf aphids on the undersides of the leaves were sprayed so that only the upper part of the leaves was affected. After 48 hours, the action was checked on the leaf aphids located on the underside of the leaves.

   The results obtained have been collated in the following table:
 EMI34.4
 
<tb> Concentration <SEP> of <SEP> the <SEP> slurry <SEP> Effect <SEP> on <SEP> the <SEP> aphids <SEP> of
<tb>
<tb> to <SEP> spray <SEP> - <SEP> - <SEP> leaves <SEP>
<tb>
<tb> Example <SEP> Example <SEP> 2
<tb>
<tb>
<tb>
<tb>
<tb> 0.08% <SEP> ++ <SEP> ++
<tb>
<tb>
<tb>
<tb>
<tb> 0.04% <SEP> ++ <SEP> ++
<tb>
<tb>
<tb>
<tb> 0.02% <SEP> ++ <SEP> ++
<tb>
 

 <Desc / Clms Page number 35>

   D. To determine the toxic effect upon ingestion of the compounds according to Examples 1 and 2, poplar leaves were dipped in spray slurries which contained 0.04% active substance.

     After the leaves were dried, they were fed to caterpillars of the fourth instar larvae of the poplar spinner hawk (Stilpnotia calicis). After 36 hours, the toxic effect was determined by ingestion. In the case of the preparation according to Example 1 all the caterpillars were dead and in the case of the preparation according to Example 2 9 out of 10 caterpillars were dead.



   In preparing spray agent concentrates, other wetting agents and emulsifiers other than those mentioned above can also be used. It is possible to envisage non-ionogenic products ;, for example condensation products with ethylene oxide of aliphatic alcohols, amines or carboxylic acids comprising a long-chain hydrocarbon residue having approximately 10 to 30 carbon atoms. carbon, such as, for example, the condensation product of octadecyl alcohol and 25 to 30 mol of ethylene oxide, or that of soybean fatty acid and 30 mol of ethylene oxide, or that of technical oleylamine and 15 mol of ethylene oxide, or that of dodecylmercaptan and 12 mol of ethylene oxide.

   Among the emulsifiers with anionic activity which can be used, we will mention

 <Desc / Clms Page number 36>

 the sodium salt of dodecyl alcohol sulfonic ester, the sodium salt of dodecylbenzenesulfonic acid, the potassium salt or the triethanolamine salt of oleic acid or of abietic acid, or mixtures of these acids, or the sodium salt of a petroleum sulfonic acid.



   Instead of isopropanol, other solvents can also be used for the preparation of spray agent concentrates, for example ethyl alcohol, methanol, butanol, acetone, methyl ethyl ketone, methyl cyclohexanol. , benzene, toluene, xylene, kerosene, petroleum fractions. It is of course also possible to use mixtures of various solvents.



   Example 20
20 parts of the product obtained in Example 1 are mixed with 9 parts of chalk and 1 part of a wetting agent. A spray powder is obtained which, when suspended in water, is used to prepare a spray slurry. If plum trees are treated with such a slurry containing 0.04% active substance, a good result can be obtained with respect to plum hoppers (Hoplocampa flava and minuta).



   Example 21
One part of the product obtained according to Example 2 is mixed with 99 parts of talc. We get an insecticide

 <Desc / Clms Page number 37>

 powdery which is suitable for powdering vines to combat first and second generation grapevine worms. The talc can also be replaced totally or partially with sulfur, in which case the preparation also becomes effective against powdery mildew. Instead of talc, it is also possible to use another powdery carrier material, such as chalk, bentonite, kaolin or mixtures of these substances.



   Example 22
If a spray mixture is used containing, per liter, 1 g of zinc-dimethyl dithiocarbamate, 0.04 g of compound No. 1 of the table of Example 6, and 0.08 g of compound No. 20 , for the summer spraying of fruit trees, good results are obtained in the fight against leaf aphids and scab (Fusicladium).



   Example 23
 EMI37.1
 -.¯..¯¯ ..., ¯¯¯¯¯
Hop plants are sprayed with a slurry containing 0.04% of the compound obtained according to Example 2. After a short time, all the hop plants are freed from leaf aphids and red spider mites (Tetranychidae).

 <Desc / Clms Page number 38>

 



   Example 24
With the compound of Example 2, good results can be obtained in the control of harmful organisms when the plants are protected by spray slurries containing from 0.02 to 0.004% of the active substance. the following pests that had not yet been mentioned in the previous examples = pear psyllid (Psylla pyricola), greenhouse thrips (Heliothrips haemorrhoidalis), dogwood lecanium (Eulecanium corni), oriental fruit moth peach (Cydia molesta), cotton leaf worm (Prodenia litura), hyponomeutes (Hyponomeuta malinella and padella), cherry blossom moth (Argyresthia ephipella).



   Example 25
When examining the action on leaf puperons following the method described under B in Example 19, all of the compounds shown in the table of Example 6 show good to remarkable effect.



   When examining for toxicity by ingestion (test device D of Example 19), the compounds of, Examples 3, 4, 6 and Nos. 3, 11, 12 and 13 of the table of Example 6 are found to be effective to very effective.



   The compounds shown in Example 11 have a systemic action (Test Device A of Example 19).


    

Claims (1)

Claims. 1. As new industrial products: 1) New organic compounds of the general formula: EMI39.1 in which R, R1, R3 and R4 represent alco- EMI39.2 yllcs, cycloalkyls, aralkyls or heterocyclics optionally substituted, R and fil 'on the one hand, and R3 and R4, on the other hand, possibly also being members of a ring system, R3 and R4 possibly being besides denoting hydrogen, R2 represents hydrogen, an alkyl residue or a halogen atom, R5 represents the residues -CN, -CO-Rg or EMI39.3 EMI39.4 (Rg denotes an alkyl, aryl or heterocyclic residue), X and Y represent-0-, -S- -NH or -N-R and Z represents oxygen or sulfur, and n and m represent integers with a value at most equal to 2; or compounds of the general formula <Desc / Clms Page number 40> EMI40.1 EMI40.2 in which R, RIs Rp, R3 'Rlll Rg, xyz Y, Z, ruz. and laugh have the meaning given above, 2) Compounds such as those defined above and corresponding to the general formula EMI40.3 EMI40.4 in which R. R 1 represent low molecular weight alkyl radicals comprising from 1 to 4 carbon atoms, and R3 and R4 represent hydrogen or also low molecular weight alkyl radicals comprising from 1 to 4 carbon atoms . 3) The compound of formula EMI40.5 4) The compound of formula <Desc / Clms Page number 41> EMI41.1 en 0 COCH3- 01:13 "'" CH3 OH 0 / / PC-Cl ". 0 H" -7 r! H 0 "/' pOC Il 3 C3 C wN 2 5 v:.; 0 cel S" c21: 15 è-N / 02H5 025 5) 'The compound' of formula CH, 00H3 OH30 3 "PC-Cl ####) p-oc OH5O C-NHCH, CÏÏ3 2ci 0 -NNgiCH3) t 6) The compound < 3rd formula CH 0 CoCi3 OH 0 CH3 ..cC. JCH- oC OH:.; 0 bN - CH "CH:.; O 0 CC7. 0 3 C-N \ CH, CT 3 \! H (3 CH3. CH, \ chez 7) Preparations for the control of harmful organisms which contain as active substance a compound such as those defined under 1 to 6. II. A process for combating harmful organisms, characterized in that a compound such as those defined under 1 to 6, or a preparation such as that defined under 7, is used for its implementation. III. A process for the preparation of new organic compounds of general formula <Desc / Clms Page number 42> EMI42.1 EMI42.2 in which R, R]., R3 'R represent aloyl, cycloalkyl, axa.cot.?cua arylic or heteracyclic, optionally Bubatitu6s, R and Rp d 9.uz. on the one hand, and R3 and R4 'on the other hand ,, may also be members of a cyclic system, R3 and R4 may also be * âés.i. 5 & or hydrogen, R2 represents 1 hydrogen, a rest *? alkyl or a halogen atom, E5 repJ; .0;: lte rE ". '' I;: '3 -ON, -CO-R6, -COOR6 or EMI42.3 EMI42.4 (R6 denotes an alkyl residue, F.iqlxe or {t.éoûy-.lque), X and Y represent -O-, -S-, -1.1-R and represent oxygen or sulfur, and n and ir are oos hildf: iLlG "t integers with a value at most equal to 2, pcr characterizes the fact that one makes react a compound of the formula <Desc / Clms Page number 43> EMI43.1 EMI43.2 .2n8 where R Rl Us mp â9 and Z have the meaning> 4.¯ :: i.w'w above and or R7 denotes an alcoholic residue of Î); .- HJ molecular weight cosspcrtaRt from 1 to -4 atoms of carbon, on a compound of formula EMI43.3 EMI43.4 i3n that R2P R3 R and 5 have the meaning given above and where H1 denotes a halogen atom such as bromine or preferably chlorine with elimination of a compound of Ï-Hale foxrals or that a halogen atom is reacted. compound e-3 formula. EMI43.5 EMI43.6 vl where 9 nJ) â3f, 2 Y and Z have the meaning,;, ("i11,, e plus 11 <1 \ ,, 11 :; 8. or designates it MM. random metal lia e .-. reference the aoJ: 1UiÏi su? - a. cosiposed of formula EMI43.7 <Desc / Clms Page number 44> in which R2, R3, R4, R5 and Hal have the meaning EMI44.1 given above oUj, loMquo R2 aéz1s [. hydrogen or an alkyl residue, which is carried out as follows: EMI44.2 @e present process can also be characterized by the following points: 1) A compound of formula is reacted EMI44.3 in which R, R1 and R7 represent low molecular weight alcoholic residues comprising from 1 to 4 carbon atoms, on a compound of formula EMI44.4 EMI44.5 in which R and R4 represent hydrogen or low molecular weight alkyl residues comprising from 1 to 4 carbon atoms. 2) Triethyl phosphite is reacted on EMI44.6 diethylam. of dichloraoetylaeetic acid. 3) Reacting trimethyl phosphite on EMI44.7 dïchloracitylaceous acid diethylamide4q, * Ic. <Desc / Clms Page number 45> EMI45.1 4). Trimethyl phosphite is reacted with EMI45.2 dichloroacetylacetic acid monoraethylamide. 5) Trimethyl phosphite is reacted with dichloroacetylacetic acid düsopropylamide.