DE1900169A1 - Organic phosphorus compounds and insecticidal compositions containing such compounds - Google Patents

Description

Insecticidal compositions containing organic phosphorus compounds and similar compounds

This invention relates to organic phosphorus compounds and insectioid masses containing them.

The organic phosphorus compounds according to the invention have the general formula:

O
AR ²

ir-OH-SEYC OR ¹ ) ₂

I »

; -O = O

in which Y is 0 or S, A is 0 * S, R ^ N or R ⁶ OOU, R ¹ is OH ₃ or O ₃ H ₅ , R ⁶ is OH ₃ , O ₂ H ₅ or O ₃ H ₇ is, and. R, R, R. And R ^ are equal to H or OH ₃ , wherein for the case (1) that A is equal to R ⁵ N, at least one of the symbols R and R equal to OH ₃ and at least one of the symbols R ⁴ and R ^{5 is} equal to H, and for the case (2) that A is equal to R ⁶ OOF, R ^{2 is} equal to H.

The compounds of the invention are against various

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Insects Toxic All of these compounds are opposite certain insects also possesses contact poisons * compared to a number of the compounds according to the invention certain insects have a systemic toxicity, said compounds of plants through the root systems, in many lalls also absorbed through the foliage and through the Plant can be transported through to growing tips, where their toxicity to sucking insects and the like acts that attack the plants »Accordingly, the compounds according to the invention have a usefulness as Insectioid

The compounds of the invention and the reactions to Their production is illustrated by the following examples, in which all percentages refer to the Take weight "

example 1
Q «0-Dimethyl-S '" (1 "methyl) ^ 2 ₀ 4 ^ imidazolidinedione>« 3-yl) methyl->

phosphorodithioate

A mixture of 285 g of 1-methyl ~ 2.4 ~ imidazolidinedione, 80 g

paraformaldehyde and 1.0 g of barium hydroxide are melted

and heated at 90 ⁰ G for one hour. The melt is in

1200 cm ^{5 of} methylene chloride is brewed and treated with 550 g (2.64 mol) of phosphorus penta chloride at ⁰ ° O. After 18 hours at room temperature, the solvent is removed and the crude mixture is distilled, giving 3o.14 g of 3-chloromethyl-i-methyl -

2 «4-imidazolidinedione with a boiling point of 155 ° ö / 4.0 mm result in * Analysis» Found Eq 21.7 $> (21.8 # 01 =! Theory).

A mixture of 9.8 g of 3-chloromethyl-1-methyl-2 _e 4-imidazolidinedione and 11.0 g of ammonium OO-dimethyl dithiophosphate in 50 om ⁵ acetonitrile is 10 hours at 25 ° 0 and then 3 hours at 60 ⁰ G stirred. The mixture is then poured into 200 cm

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Water »The organic layer is taken up in 100 m of benzene, the benzene solution is washed with 5% aqueous sodium bicarbonate solution and then with water and dried. After the benzene has been distilled off, 16.1 g of oily OoO-dimethyl-S- ( 1-methyl-2 <, 4-imidazolidinedion-3-yl) methyl dithiophosphate, the analysis of which gives 11.0 $ P (10.9 $> P = theory) «,

Example 2. '

OoO-diethyl-S- (1-methyl) -2 »4-imidazolidinedion-3-yl) methyldithiophosphate

The ethyl ester corresponding to the product of Example 1 is prepared by following the procedure of Example 1 and that corresponding ammonium-OcO-diethyl-dithiophosphate as a reactant applies »

Example 3

0> 0-Dimethyl-S-Ci- (1'-methyl-2 "_< .4 ^t -imidazolidinedione""3'-yl) ethylH dithiophosphate

A mixture of 57 g of i-methyl ^^ - imidazolidinedione, 46.2 g of ethylene carbonate and 0.3 g of sodium bicarbonate is ^{heated to 150 to 200 0} O until the 00 ,, evolution ceases. The product mixture is cooled down at 300 cm Pyridine diluted and treated with 60 g acetic anhydride. After heating this Gremisohes at 100 ⁰ O for 4 hours, it is freed from the solvent and the crude 1-methyl-3- (2'-aoetoxyethyl) - is distilled. 2 # 4-imidazolidinedione to give 88.2 g of purified product. The boiling point is 130 to 136 ° 0 / 0.2 mm and the analysis gives .13.9 $ nitrogen (theoretical value 14.0 #)

At 0.5 om ⁵ per minute at 55O ⁰ O 6o g of 1-methyl-3- (2 "- aoetoxyethyl) -2,4-iniidazole $ indione are added to a packed tube 366 × 2.54 om · The crude pyrolysate is distilled and gives 18 g of 1-methyl ~ 3-vinyl-2 _e 4-imidazolidinedione

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w 4 **

from the boiling point 86 to 89 ° C / 0.3 mm to a solution of 7.6 g

in 10 cm of benzene is added dropwise 10.3 g OoO Dimethyldithiophosphorsäure at 25 ° 0 with air cooling within 18 hours add "The resulting solution is washed with 50 cm benzene _ff diluted with two 50 om servings a 5- ^ weight aqueous Sodium bicarbonate solution and then washed with water and dried. The benzene is distilled off and 15.7 oily OoO ~ dimethyl-S ^ 1- (1'-methyl-2 ¹ _o 4 ^t -imidazolidinedion-3'-yl)] - A * ethyl dithiophosphate · Its analysis results in 10.9 1 ° P (10.4 i ° P = theory) ο

Example 4
OO-diethyl-S-Li- (I '-methvl-2' _O 4 ^! -Imidazolidinedione-3 '-yl) -ethad]

dithiophosphate

This compound prepared as in Example 3, using O ₀ 0 ~ diethyldithiophosphoric acid as the reactant. The analysis of the product gives 9 | 9 # P (9.5 $ P = theory) ·

Example 5
0βO-diethyl-S-11-methyl-2 _β 4-imidazolidinedione-3-y] J-methyl-thio _:

phosphate

To a solution of 20.6 g ammonium OEO-diethyl thiophosphate in 100 cm dimethyl sulphoxide, are employed gradually at 25 to 37 ⁰ O 3 16.2 g "0hlormethyl-1-methyl-2O4-imidazolidinedione (as prepared in Example 1 ). Awake for 18 hours at 25 ° 0, the solution is ^{heated for 3 hours at 60 0} O and then cooled. The product is worked up by diluting it with 1000 cm of water and extracting it with methylene chloride. The organic layer is washed with water and dried and the product is recovered 0 · O-diethyl-S- (1-Methy1-2 «4-imidazolidinedion-3-yl) -methyl-thiophosphate by distilling off the methylene chloride« The yield is 2505 g of a yellow oil, which in the

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Analysis 1ο.4 $ P resulted in (1ο.5% P = theory) ₀

Example 6

0 «, 0-3) iiiiethyl-S- (1-methyl-2,4-imidazolidinedion-3-yl) -methyl» thiophosphate

Following the procedure of Example 5 when used of ammonium-OoO-dimethyl-thiophosphate as a reactant, is obtained with a theoretical yield of $ 96 the O * O-dimethyl ~ S- (1 ~ methyl ~ 2 <, 4-imidazolidindion-3-yl) -Methy! thiophosphate, which in the analysis was 11.8% P and 10.2 # N resulted in (11.6 $ Pj 10.4 # N = theory) *

Example 7
OoO-Dimethyl-S- (1.5-Dimethyl-2 «4-imidazolidinedione ~ 3 ~ yl) -Methy:

dithiophosphate .

1o5-I) imethyl-3-qhloromethyl-2,4-imida250lidinedione is prepared in the same way as described above for 3-Ohloromethyl-i-methyl-2o4-imidazolidinedione, using 1 _# 5-dimethyl <2ο4-imidazolidinedione instead of i -Methyl-20 4-imidazolidinedione used. The product distills at 109 ° 0 / 2.0 mm «

A mixture of 11.6 g of 1 _e 5-dimethyl-3 "ohloromethy 1-2 · 4-imidazolidinedione and 11o5 g of ammonium" 0o0-dimethyl-dithiophosphate in 100 om ^ acetonitrile is ^{heated for 8 hours at 6O 0} O "This is distilled Acet / onitrile, dilute the product with 100 cm of ether, wash with 5% strength aqueous sodium bicarbonate solution and then with water and dry. When the ether is distilled off, 11.0 g of 0 _o 0-dimethyl-S- (1,5-dimethyl2,4-imidazolidinedion-3-yl) methyl dithiophosphate with an analysis of 11.9 $> P ( 1O | 4 # P = theory) _o

Example 8
OoO-Pimethvl-S- L1- (2 '_<> 4 ^t -imidazolidinedione ~ 3 «-> yl) ethyll -di -

thiophoBphat

3-vinyl-2ο4-imidazolidinedione is processed in the same way

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ride the 1-methyl-3-vinyl-2 _e 4 ~ imidazolidinedione _{as described above, using 2 O} 4-imidazolidinedione instead of 1-methyl * - 2 <> 4 - imidazolidinedione »The product distills at 155 ° O / 1.0 mm and melts after recrystallization from isopropanol at 87 to 89 ° Co

A mixture of 2 ₍₃ g of 3-vinyl-2.4-imidazolidinedione and 5 cm OO-dimethyl-dithiophoaphoraäure heating them to control carefully and gradually to 95 0 with provisions for cooling to the exothermic reaction ₀ The reaction is then 3 hours at 80 to 90 ⁰ O continuing the reaction mixture is cooled, diluted with 40 cm of benzene, washed with 5 ji aqueous Natriumbicarbonatlö'sung and with water and then dried Man the benzene is distilled off and gains 5 »6 g of solid OoO-dimethyl-S- £ 1- (2 · o4'-imidazolidinedione-3 ^! -Yl) -äthyljf dithiοphosphatο This solid melts after recrystallization from isopropyl alcohol at 110 to 112 ° 0 «Its analysis gives 10.9 # P (10.9 # P = theory ) «,

Example 9.

OoO-diethyl-S- Ci- (2 ».4 ^t -imidazolidinedione-3 ^l " .vl) -ethyl] -dithio-

phosphate

Using 0 ₀ 0 ~ diethyldithiophosphoric acid in Example 8, the OoO -diethyl-S- £ "i- (2 · _e 4'-imidazolidinedione-3'-yl) -ethyl] -dithiophosphate is obtained as an oil, which in the analysis showed 11.0 # P (10.0 # P = theory) »

Example 10

Oo 0-Dimethyl-S- (2.4 "03cazolidinedione ~ 3 ~ yl) -Methyl-dithiophosphate A mixture of 17 _f 2 g 2,4-oxazolidinedione, 6.0 g paraformaldehyde and 0.1 g Ba (OH) ₂ is melted and heated for one hour at 90 ° G «The melt is introduced into 100% methylene chloride and treated with 36 g of phosphorus pentachloride. The mixture is left to stand overnight at 25 ° 0 and removed

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Solvent. The residue is treated with cold water and recrystallized from isopropanol to give 16.3 g 3-0hlormethyl-2O4-oxyzolidindion result, the melting point of 68-69 ⁰ O i and its analysis 23.7 »chloro yield (theory:

oo 7 oL \
"ff /» / ·

A mixture of 7.5 g 3-0hlormethyl-2 _e 4-oxazolidinedione and 9.6 g of ammonium OEO-dimethyl dithiophosphate in 40 cm of water for 8 hours at 40 to 50 ° O The organic heated sliding: is taken up in benzene When the solvent is removed, 12.2 g of OoO-dimethyl-S- (2,4-oxazolidinedion-3-yl) -methyl-lithium phosphate remain as a colorless oil back, which results in the analysis 11.5 1 ° P (11.4 i ° P »theory),

Example 11

OoO ~ diethyl ~ S "(2,4 ~ oxazolidinedion-3-yl) ^ ethyl ~ dithiophosphate If the procedure of Example 10 is followed, 11.8 g of ammonium OoO-diethyl dithiophosphate are added to 7.5 g of 3-chloromethyl 2o4-oxazolidinedione and 14.4 g of O # O-diethyl-S- (2c4-oxazolidinedion-3-yl) methyl dithiophosphate are obtained as a colorless oil which, on analysis, showed 9.8 <fo P: ( Theory: 10.3 # P) o

Example 12

0,0-Dimethyl-S "(5" Methyl-2,4-oxazolidinedion ~ 3-yl) -Methyl-'di '·' thiophosphate

Following the procedure of Example 10, 12.3 g of 3-chloromethyl-5-methyl-2o4-oxazolidinedione, which was prepared in an analogous manner, are reacted with 14.4 g of ammonium OO-dimethyl dithiophosphate and 17.4 g are obtained O, O-Dimethyl-S- (5-methyl-2,4-oxazolidinedion-3-yl) -Methyl "dithiophosphate as an oil, which in the analysis resulted in 11.2% P (theory 10.9 $ P)"

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19Q0169

Example 13
O »O-diethyl-S- (5-methyl-2,4-oxazolicl.indion ~ 3-yl) -methyl-dithio

phosphate

Following the procedure of Example 10, 12.3 g of 3-chloromethyl-5-methyl-2 _e 4-oxazolidinedione, which was prepared in an analogous manner, are reacted with 17.6 g of ammonium OeO diethyl dithiophosphate and one receives 18.8 g of OoO-diethyl ~ S «(5 ~ methyl-2o4-oxazolidinedion-3-yl) methyl dithiophosphate as an oil with the analysis 9 _f 9 # P (theory 9.1 /" P) "

Example 14 O «O-dimethyl-S" Li * »(5'-methyl-2 ', ^' Ethyl dithiophosphate

3 ~ Yinyl "5-methyl ~ 2,4-oxazolidinedione is prepared from 5« · methyl 2e4 ~ oxazolidinedione according to the procedure for preparing 3 ~ vinyl-2o4- "oxazolidinedione in the example below 18 _O

A solution of 11.5 g of OeQ-dimethyl-dithiophosphoric acid and 8.4 g of 3 «vinyl-5-methyl-2o4-oxazolidinedione in 50 cm ^{5 of} benzene is heated at 50 ° 0 for 3 hours and the benzene is distilled off, finally 3 Heated at 90 ° for hours. »The product is redissolved in benzene, washed with 5 # aqueous sodium bicarbonate and water and dried.» When the benzene is removed, 15 »3 g of O» O-dimethyl-S ~ £ ^ 1- (5'-Methy.1-2 ¹ • 4 ^! -Oxazolidinedione-3'-yl) -ethyl] -dithiophosphate back, which is an oil and gives 11.2 # P on analysis (1o, 4 96 -p theoretically ) e

Example 15 Q. O-diethyl-S-C1 ■ (5'-methyl-2 '. 4'-oxazolidinedione ~ 3' - di thiophosphate

According to the procedure of Example 14, 13.5 g of 0.0 Diethyl dithiophosphoric acid with 8.4g 3-vinyl ~ 5-methy1-2.4-

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oxazolidinedione implemented. 17.5 g of OO-diethyl-S - /! - (5'-methyl-2 ¹ .4'-oxazolidinedione-3 ^l -yl) ethyl-7'-ditliioplioapliat are obtained as an oil with the analysis 9.9 $ P (theory: $ 9.5 P)

Example 16

0.0-Dimethyl-S- (2o4-oxazolidinedion-3-yl) methyl-thiophophate A mixture of 20.2 g of 2,4-oxazolidinedione, 6.6 g of P-araformaldehyde and 0.1 g of Ba (OH) ₀ is melted and at 90 for one hour ⁰ G er

■ 3
heats. The melt is brought in 100 cur methylene chloride and are added at 0 to 10 ⁰ O 18.2 g of phosphorus added "The mixture is allowed to overnight at 25 ° 0 stand, the methylene chloride solution is decanted and the solvent is removed. The residue is washed with water and recrystallized. Bs result 16.7 g of 3-bromomethyl-2.4 ~ oxazolidinedione of melting point 63-64 ⁰ G. An NMR spectrum is consistent with its structure _e

A mixture of 15.0 g of 3-bromomethyl-2,4-oxazolidinedione and 13.0 g of ammonium OO-dimethyl thiophosphate in 100 cm ^{5 of} acetonitrile is 48 hours. held at 25 ° 0 and ^{heated at 60 0} G for 4 hours *. The mixture is filtered, the acetonitrile is distilled off and the residue is dissolved in methylene chloride. The methylene chloride solution is filtered and the filtrate is freed from solvent by heating it under reduced pressure. The residue from this treatment is 15.3 g'0.0-dimethyl-S- (2 «4-oxazolidinedion-3-yl) methyl thiophosphate with an analytical value of 12.6 $ phosphorus (12.2 $ P is the theory).

Example 17

0.O-Diethyl-S- (2.4-oxazolidinedion-3-yl) methyl-thiophosphate A mixture of 15.0 g of 3-chloromethyl-2.4-oxazolidinedione and 20.4 g of ammonium OO-diethyl thiophosphate in 100 cm ^{5 of} dimethyl sulfoxide is 48 hrs. at 25 ⁰ C and kept heated at 60 ⁰ O 3 · h. The mixture is diluted with 400 cnr ⁵ water and extracted with methylene chloride. The methylene chloride extract is dried and freed from solvent, 18.3 g of 0.0-diethyl-S- (2.4-oxa-

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- ίο -

zolidindion-3-yl) methyl thiophosphate is obtained, which in the Analysis 11.1 $ P gives "(theory: 10.9 $ P)"

Example 18

0.0 »>Dimethyl" S- / T- ( 2 '.4' -oxazolidi ndione-3 ⁸ -yl) ethyl7-dithio phosphate

A mixture of 202g 2,4-oxazolidinedione, 185g and 1.0g Äthylenearbonat Natriumbioarbonat is heated for 3 hrs. At 155 to 160 ⁰ G. The melt is cooled, dissolved in 500 cm of pyridine and treated with 220 g of acetic anhydride. This mixture is heated for 3 hrs. At 100 ⁰ O removed the pyridine and the residue is distilled at 3 to 8 mm Hg pressure to yield 148, Qg
3 ~ (2 ^t ~ acetoxyethyl) ~ 2 _e 4'-oxa25OlidindiQn with boiling point 144 bia

150 ⁰ O result, which in the analysis shows 7.8 $ nitrogen (theory: .7.5 $) β

This acetate is added to a tube packed with coils of stainless steel and is heated to 580 ⁰ O. The pyrolysate is distilled and gives 51.1 g of 3-vinyl-2,4-oxazolidinedio with a boiling point of 100 to 1O5 ° O / O.2mm, which on analysis shows 10.8 $ nitrogen (Theories 10.8 $).

A mixture of 17,0g OO-dimethyl-dithiophosphoric acid and 8, 3-vinyl-2,4-oxazolidinedione. 8 hours at 90 ⁰ C is heated. That
The product is dissolved in benzene, washed with 5% aqueous sodium bicarbonate and water and dried. When the benzene is removed, 14.2 g of 0.0-dimethyl-S- / T- (2'.4 »-oxazolidinedione-3 '~ yl) ethy2j7-dithiophosphate, which is an oil, remains
Analysis yields -10.4 $ P (Theories 10.9 $ P).

Example 19 OO-diethyl-S - / T ~ (2 '.4'-oxazolidinedione-3'- phosphate

According to the procedure of Example 18, 20.0 g of OO-diethyl dithiophosphoric acid are reacted with 9.0 g of 3-vinyl-2,4-oxazolidinedione. 21.9 g of OO-diethyl-S ~ / T- (2'.4'-oxazolidine ~ are obtained
dion-3-yl) ethyl7-dithiophosphate as an oil with the analysis

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10.6 ^ 6 P (theory: 9.9 $ P).

Example 20
OQ-Dimethyl-S- (2.4-thiazolidinedion-3-yl) methyl dithiophosphate

A mixture of 225g 3-chloromethyl-2,4-thiazolidinedione and 290g

■ 3 ammonium OO-dimethyl dithiophosphate in 1500 cm of water is ^{stirred at 50 0} C for eight hours. The organic layer is brought in

3 3

1000 cm of benzene. The benzene solution comes with two 100em servings

^{1 line}

5 $ iger NaHOO · *, and washed with two 100 cm portions of water After removing the benzene, 323.3 g of a pale yellow oil are obtained, which O »O-dimethyl-S- (2 <, 4-thiazolidinedion-3-yl) methyl dithiophosphate, which when analyzed gives phosphorus $ 11.5. The theoretical value for phosphorus is $ 10.8.

Example 21
0.0-diethyl-S- (2 <= 4-thiazolidinedione-3 ~~ yl ) methyl dithiophosphate Following the procedure of Example 20, 16.5 g of 3-chloromethyl-2,4-thiazolidinedione and 30 g of ammonium diethyldithiophosphate give the 0.O- Diethyl S- (2,4-thiazolidinedion-3-yl) methyl dithiophosphate which, when analyzed, shows 10.1 $ phosphorus. The theoretical phosphorus value is $ 9.7.

Example 22. .

O.O-pimethyl-S- (5-methy1-2.4-thiazolidinedion-3-yl) methyl-dithiophosphate

Following the procedure of Example 20, 9.0g ^: 3-chlorometh3ri ~ 5 ~ methyl-2,4-thiazolidinedione and 10.5g ammonium OO-dimethyldithiophosphate give 10.8g of an oil which contains 0.0-dimethyl-S- (5- methyl-2,4-thiazolidinedion-3-yl) methyl-dithiophosphate and the analysis shows 9 »7 $ phosphorus. The theoretical phosphorus value is $ 10.3.

Example 23
0.O-Diethyl-S- (5-methyl-2.4-thiazolidinedion-3-yl) methyl-dithio.

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~ 12 -

phosphate

By following the procedure of Example 20, 9 »Og 3-chloromethyl-5Hmethyl ~ 2 _e 4 ~ thiazolidinedione and 12.5 g ammonium OO-diethyl dithiophosphate, 11.8 g of an oil which OO-Uiäthyl-S- (5- methyl «2.4-thiiazolidinedion-3-yl) methyl-ditliiophosphat istο The analysis shows 9.4 $ phosphorus. The theoretical one

Value for phosphorus is 9,

Example 24

0.0 ~ dimethyl-S ~ (5 . 5-dimethyl-2,4-thiazolidinedione-3 ~ yl) methyld i thi ο phos phat

Following the procedure of Example 20, give 15.5g of 5,5-dimethyl-3-ahlomethyl-2o4-thiazolidinedione and 1Έ>, 5g of ammonium-OO-dimethyl-dithiophosphate, 21.4g of an oil which is 0.O-dimethyl-S- (5.5-dimethyl-2.4-thiazolidindion-3-yl) methyldithiophospha "t is ₀ The analysis gives $ 8.5 phosphorus. The theoretical phosphorus value is $ 9.9.

Example 25

0.0-diethyl-S- (5.5-dime thvl-2.4 ~ thiazolidinedione ~ 3-yl) methyldithiophosphate

Following the procedure of Example 20, using 19 »5 g of ammonium O.O-diethyl dithiophosphate instead of the O.O-dimethyl salt, 23.9 g of an oil are obtained which O.O-diethyl-S- (5.5-dimethyl-2,4-thiazolidinedion-3-yl) methyl dithiophosphate is. This results in the analysis of $ 9.5 phosphorus. The theoretical one Value for phosphorus is $ 9.1

Example 26

Q.0-Dimethyl-3 - (2 »4"thiazolidinedione-3'-yl) methyl "dithiophOBphat A mixture of 16.6 g of 3-chloromethyl-2,4-thiazolidinedione and 17.7 g of ammonium 0.0-dimethyl-thi ο phosphate in 100% water is ^{reacted at 50 0} O for 8 hours. 6.8 g of OO-dimethyl-S- (2,4-thiazolidindiori-3-yl) methyldithiophosphate _{1 are obtained,} which is obtained by extracting with benzene and washing with aqueous sodium bicarbonate

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and distilling off the benzene wins. It is an oil which the analysis results in 10.0 $ P and 4.6 $ N (theory: 11.49ε Ρ and 5.1 $ N).

Example 27

0.0 ~ jimethyl-'S '/ T ~ (2O4'-thiazolidinedione-3> »yl) eth. Yl7 ^=: dithio- <phosphate

A mixture of 7.2g 3 ~ vinyl-2 _o 4-thiazolidinedione and '15t8g 0οO-dimethyl-dithiοphosphoric acid' is ^{heated for 12 hours at 50 to 60 0} O (caution: if ^{it is heated to 90 0} G, it decomposes Exothermic mixture) The mixture is diluted with 50 cm of benzene, washed twice with 50 cm of 5% NaHCO 3 and with water and dried. The benzene is removed and yields 15.0 g of an oil which is 0.0-dimethyl-S- / T- (2'.4 '~ thiazolidinedion-3-yl) ethyl7 * -dithiophosphate and which on analysis is 11.4% phosphorus results. The theoretical phosphorus content of this product is 10.3 $ »·

Example 28

0.O-diethyl ~ S " / T- (2 ' _o 4'-thiazolidinedion-3'-yl) ethy l T-dithiophosphate

Following the procedure of Example 27, if one uses 18.6 g of "OO-diethyl-dithiophosphoric acid instead of 0.0-dimethyl acid, 17.6 g" of an oil which OO "diethyl-S- / T- (2'.4 ' -thiazolidinedione-3 ^! -yl) äthyl7-dithiophosphate and which on analysis shows a phosphorus content of 10.2 $. The theoretical phosphorus value is 9 | 5 $ »

Example 29
0 .Q-Dimethyl-S »- (1-acetylhydantoin-3-yl) methyl-dithiophosphate or similar

Production of 1-acetylhydantoin - A solution of 300g hydantoin and 30Og acetic anhydride is refluxed for 3 hours. The excess anhydride is removed by distillation up to a vessel temperature of 80 ° C / 18 mm. The residue is heated to reflux with 600 cnr water. When leaving

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190016g

-H-

cool to 211,3g of white crystals of melting point 92 to 141 form Cj ⁰ N $ 17.3 (Theory for ^1-β acetylhydantoin H ₂ O 17.5 $) "Recrystallization from alcohol gives 156g of product of melting point 146 to 148 ⁰ Cj N $ 19.5 (theory: $ 19.7) »

Production of 1 ~ acetyl-3-hydroxymethyl-hydantoin - A suspension of 59 g of 1-acetyl hydantoin in 88 cm of water, which contains 44 g of 37% aqueous formaldehyde, is heated to homogeneity (about 60 ⁰ O in 15 minutes). When cooling down, 30g of white crystals with a melting point of 103 to 104 ° Gj Ή 16.2 $ and OH (Zerewitinoff) 10.4 $ (theory 16.4 or 9.9 $) »

Production of 1-Ao etyl-3-ohlormethyl-hydantoin - To a sus-

. W U

28.3 g of 1-acetyl-3-hydroxymethylhydantoin in 51 cnr methylene chloride, which is cooled to 10 to 15 ° C., are added _{within 30 minutes to 34.4 g of POl 5.} After standing over Naoht at room temperature, the methylene chloride is removed at room temperature under suction vacuum. Cold water is added to the residue. The solid removed by filtration weighs 25.2 g and has a melting point of 108 bid 110 0. Cl 18.7 $ (theory: 18.7 $).

Production of OO-dimethyl-S-'f 1-aoetylhydantoin-3-yl) methyldithiophosphate - A solution of 12.5g 1-acetyl-3-chloromethylhydantoin and 13.4g ammonium dimethyldithiophosphate in 100 cm acetone is 8 Hours under reflux, during which time NH, Cl precipitates. The cooled suspension is poured into water and the organic layer extracted with ether. The A'therlösung one wäsoht with 5 $ aqueous NaHCO ^ solution and then with water, dried over anhydrous sodium sulfate and the solvent is removed by distillation at 18mm pressure to a pot temperature of 80 ⁰ C. The residue at 80 ° C / 5mm. skimmed off and there remain 14.2 g of a yellow, viscous liquid; N $ 8.6 and P $ 10.8 (theory: 9.0 and $ 10.0, respectively. The NMR and infrared absorption spectra are in agreement with the proposed structure.

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- · 15 -

Example 30 O. O ~ Dimethyl-S- (1- aoetyl-5,5-dimethylhydantoin-3-yl) methyl

dithiophosphate

In accordance with the procedure of Example 29, 11.8 g of 1 ~ aoety3-3-chloromethyl-5,5-dimethylhydantoin are obtained Reacted from melting point 103 to 1O5 ° O with 9 »2g ammonium dimethyl dithiophosphate. Man receives 12.6 g of O.Q ~ dimethyl-S «(1-aoetyl-5,5-dimethylhydantoin-3-yl-methyl-dithiophosphate. Analysis gives $ 8.6 P.

Example 31
OO-Jimethyl-S'-C 1-aoetylhydantoin-3-yl) methyl thiophosphate A mixture of 10 g of i-acetyl-3-chloromethyl hydantoin and 9 g of ammonium dimethyl monothiophosphate in 50 cm of acetonitrile is used. Maintained under reflux for 8 hours. The cooled reaction mixture is filtered and the solvent is removed from the filtrate at 80 ° 0 / 18m] ι The residue is dissolved in hot acetone, the solution is cooled and decanted from the slurry. Removal of the solvent and skimming off at 80 ° 0 / 0.5 mm leave 12 g of a yellow, viscous liquid; P'10.3 $ and N 10.1 $ (theory: 10.4 and 9

Example 32
0.O-Dimethyl ~ 5- (1-aoetyl-5.5 ~ dimethylhydantoin ~ 3-yl) methyl-thio-

phosphate

Following the procedure of Example 31, 21 g of 1-aoetyl-3-gilomethyl-5,5-dimethylhydantoin, melting point 10-3 to 1050, are reacted with 17 g of ammonium dimethyl monothiophosphate. 19.6 g of 0 are obtained »0-Dimethyl-S- (1« Aoetyl-5 »5-dimethylhydantoin-3-yl) -Methyl« thio · phosphate with the analysis 9t9 i » P ·

Example 33 0 «« «Dimethyl-S ~ (1« «butyrylhydantoin-3" yl) methyl «» thiopliOBphate According to the procedure of Example 31, 15 g of 1-butyryl-3-chloromethylhydantoin are mixed with 11 g of ammonium dimethyl monothiophosphate in reacted with a reaction medium made from aoetonitrile · Man

909836/15 52

receives 2o.8 g of O.O-dimethyl-S- (1-butyrylhydantoin-3-yl) ~ methyl ~ tlii ο phosphates

Example 34

Q «O-diethyl-S- (i-aoetylhydantoin-3-yl) methyl thiophosphate

According to the procedure of Example 31, 10 g of 1-acetyl-3-chloromethylhydantoin are used with 11g ammonium diethyl monothiophosphate in an acetonitrile reaction medium. 11,7 g of OeO-dietliyl-S- (1-acetylhydantoin-3-yl) methyl-thiophosphate are obtained

Example 35

OoO-I) iäthyl-S-Ci-aoctyl-5o5-dimethylhydantoin-3-.yl) methyl-dithiophosphate

In accordance with the procedure of Example 31, 11.8 g of 1 «acetyl» 3-chloromethyl-5,5-dimethylhydantoin with a melting point of 103 to 1050 ° are reacted with 11.0 g of ammonium diethyl dithiophosphate. 3 »6 g of 0» 0 are obtained -Diethyl-S- (1-aoetyl-505-dimethylhydantoin-3-yl) methyl-dithiophosphate, which shows 8.6 $) P on analysis.

The compounds according to the invention are in impure or in in the purified state used as essential components of toxic, dispersible masses to influence insects A dispersible mass of this type is a concentrate consisting of the compound and an effective amount of one Dispersant consists

In the case of a solid, dispersible mass, the dispersant is a finely divided, dispersible, inert solid such as is known in the insecticide art. A typical diapergeable solid of this type is clay. A typical dispersible concentrate contains 10 to 50 # of the active, toxic By means of and $ 50 to $ 9 dispersants. In the case of a liquid dispersible mass, the dispersant is an effective amount of one or more organic ones

909 8 36/155 2

Dispersants, at least one of which is an organic, Surfactant is «Liquid Dispersible Compounds for conversion into aqueous emulsions contain an emulsifying, surface-active agent or an emulsifying mass, which comprises an effective amount of an emulsifying surfactant and an organic solvent, welci the latter is present in a concentration which is sufficient to make the mass flowable. '

The solid dispersible masses are usually also dispersible in water. In this case the mass contains toxic substances Agent, dispersible solid and an emulsifying agent in amounts sufficient to ensure a stable dispersion of the to bring about toxic agent and solid in water. One mass of this type is the well-known dispersible powder.

Suitable dispersants and emulsifiers are known to those skilled in the art and many are in Frear, Chemistry of Insecticides . Fungicides and Herbicides indicated. Suitable solid dispersants are inorganic, »They include talc, attapulgite, propylite, diatomaceous earth, kaolin, aluminum and magnesium silicates, montmorillonite, fuller's earth and their equivalents,

Dispersants which are useful in such concentrates are the known surfactants of the anionic, cationic or nonionic type, including Alkali (sodium or potassium) oleates and similar soaps, Amine salts of long-chain fatty acids (oleates), sulfonated animal and vegetable oils (fish oils and castor oil), sulfonating te petroleum, sulfonated, acyclic hydrocarbons, sodium salts of lignin sulfonic acids, alkylnaphthalene sodium sulfonate, sodium lauryl sulfonate, disodium monolauryl phosphate, sorbitol Laurate, pentaerythritol monostearate, glycerine monostearate, polyethylene oxides, ethylene oxide condensates of stearic acid, stearyl alcohol, Stearylamine, natural resin amines, dehydroabietylamine

9098 36 / TS'5'2 "-

• "• 18 ·" ·

and the like, laurylamine salts, dehydroabietylamine salts, laurylpyridinium bromide, Stearyl trimethyl ammonium bromide, Getyl « Dimethylbenzylammonium chloride and the like * The aqueous Dispersions can thus be made from the compounds themselves, from those dissolved in water-soluble or water-insoluble solvents Connections, or prepared from wettable dust »

The preferred compositions for spraying onto plants which are attacked by insects are those in which water is used as the predominant component and a compound of the invention as a subordinate component _e Such aqueous dispersions are usually prepared in this field so that si © a content of 0.5 to 10% by weight of the active agent, a concentrate composed of about 10 to 90% by weight of the active agent, about 0.5 to 10% by weight of the dispersant and 0 to 90% by weight of the inert diluent being dispersed ·

The toxic compounds of the invention are also adapted for use by low volume air spray, wherein one or more of these compounds alone or in a mixture with a minor amount of another toxic compound, such as toxaphene, dissolves in sufficient solvent to an amount equal to the weight of the whole toxic material is to be a solution having a viscosity at 25 ° 0 of 10 to 50 centipoise, preferably 20 to 50 centipoise to produce, this solvent consisting essentially of xylene and, if necessary, sufficient isophorone to effect complete solubility of the toxic agents at the desired viscosity o

The systemically active compounds according to the invention are before absorption / duroh the roots on the roots of the plants, or for absorption through the foliage, applied to the foliage of plants * These compounds are generally applied in admixture with a granulated solid carrier or

9 09836/155 2

SAD ORIGINAL

·. 19 -

with a wettable powder or as an aqueous emulsion of the compound itself, or the compound dissolved in an organic solvent or adsorbed on a wettable powder The systemically active compounds according to the invention can also be applied to the seeds themselves as wettable powders, as aqueous emulsions or as solutions in organic solvents, so that the toxic compounds The systemically active compounds can also be added to the soil after sprouts of the plants to be protected have formed ₀ This can be done by adding an aqueous emulsion which egg ne systemically active compound according to the invention with or without a solid carrier, directed at the location of the roots in the soil, the toxtic compound being carried into the soil by rain or artificial irrigation.

The toxicities of the compounds according to the invention are shown by the data given in the following tables:. light These data corresponding to each compound are obtained as follows · It is obtained from each of the Tables Compounds an emulsifiable concentrate prepares, ind'e; dissolve 1.5 parts of compound in 5 parts of benzene and 3 parts Sorbitol monolaurate polyoxyethylene derivative, Tween'20, added The concentrate obtained in this way is then dispersed in 150% of water, so that a 1-96% aqueous emulsion results. Lower concentration emulsions are obtained by adding aliquots of this emulsion with appropriate amounts of water diluted These aqueous emulsions are then tested for their toxicity to selected insects, where-

909836/1552

where the test procedure for a specific insect is the same for each compound tested. The test results are summarized in the following tables. The insect mortality values are reported as "# / #" or as "# / parts per million". The abbreviation "$ / $" refers to the percentage of the killed by the test compound in aqueous emulsion insects at the concentration which is displayed sign by the second percentage, which concentration is indicated as percent by weight of the emulsion _o The abbreviation "# / parts per million "refers to the percentage of insects killed by the test compound in aqueous emulsion at the concentration indicated as" parts per million ", this concentration being expressed in parts by weight per million parts by weight of emulsion" _e

909836/1 552

iel R ¹ OH R ² R ⁵ Tabel R ⁴ • η 5 r TSM-S • j Y ■ -. '^ο; Z, · .; of connections 90 / 0.0025 PA-S 1 systemic) systemic; G H 80 / 0.005 io / tle j. mill. I.
I. Two-spotted Mite "Systemic (two-spotted mite - OH, G ^ H ₅ - H CH H H S. μβΓ - PA iPY (0R ¹ ) ₂ 60 / 0.1 100/10 j H OH, H H S. io / io fo / jo 100 / 0.1 100/10 * ; .beisi * Oh! CH ₃ CH, H H S. 100/0 »0025 R-TSM 100 / 0.005 100/10 TSM-S ί OH, · OH, CH, H H S. 100 / 0.001 io / io 100 / 0.1 100/10 # / Tle, i.Mo ! 1 J? j
H GH H H O 100 / 0.005 10.0 / 0.0025 100 / 0.005 60 / 0.1 100/50 100/50 i 2 H CH ₃ H H O .100 / 0.001 100 / 0.001 90 / 0.1 100/10 100/50 i 3 H CH, CH ₃ H S. 80 / 0.005 100 / 0.005 100/50 100/10 : τ GH D.
H H H S. 100 / 0.001 100 / 0.001 100/10 0/50 5 OH ₃ H H H S. 100 / 0.005 100 / 0.001 100/10 100/50 ^ e MBB 70 / 0.01 100 / 0.001 (Mexican Bean Beetle) 100/10 ^ I ' ⁷ PA ·· 90 / 0.005 100 / 0.005 (Breast louse) 100/50 ; 8th R-TSM 100 / 0.005 Two-spoxed 100/50 I 9 100/08005 100/50 PA-S Mexican Bean Beetle - Systemic Pea aphid Resistant ά Mite (resistant, two-spotted Mite) ■ Pea aphid (Pea louse - i

H H ω , α CD

CM

-P CvI H CQ / O to : α » Ph ω 1 / -C Ph -ρ a f • Η - ο til ο I. • rl (χι Ο-Ο \ M. O ο P. Q) rf "Ö - ο ω I. • Ρ _κ \ α> αϊ ti H

ω • Η

α) to

CQH

I: d

0) P Q)

Q) W) • Η Q)

IS)

οοοοοοοοοο

ν- IAv- lAlALALAlAlAlA

ο ο ο ο ο ο ο ο ο ο - ^ - ο co ο

W.
O

WWW

CQ 03

W W W WM

WW OO

W W O

W O

W O

approx

WWW

tr; C-

LTk CO IA to "ΐ ii% U. 1 to W. W. W. W. X- 1 to pc W. CM O CM O Γ.) W '' ■ '■ iü cm O O O ο ο

ί>

ElO

Ci H

? i ω

'Ö -rl

rf pi

■ rl

CM to

ir \

9 0 9 0 Y o; / 15 5 2

BAD ORfGiNAL

connection of
example CHj
C ₂ H ₅ , Table 3 R ⁴ - Insect toxicity of compounds • 20th
21 CHj H
H the formula 22nd ° 2 ^Ξ 5. CHj OQ R ²
/ ^> 1
S IT-CH-SPT (OR) « 23 GHj CHj R ⁴ OH ⁵ 00 I.
*? * CD
O 24 O ₂ H ₅ jL OHj R ⁵ · JL I. 9836/1 25th CHj H
H ^σΞ 3 H . S.
HS cn
cn 26th OHj H H HS K) 27 O ₂ H ₅ Ξ H H S 28 Ξ H CHj S H OHj S Ξ H 0 CHj H S OHj HS '

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CD CX)

Compound of Example 20 21 22 23 24

25 26 2 " 28

E? Ι · Γ33 PA SAW

Table 3 (continued)

■ E? * /

HBB

H-TSM
1 ° / 1 °

PO GRW PA-S

/ $> y * / jo fl / gle, j .M.

40 / 0.025 100 / 0.005 100 / 0.005

100 / 0.05 100 / 0.005 100 / 0.005

100 / 0.05 100 / 0.01 0 / 0.01

100 / 0.05 100 / 0.005 100 / 0.01

60 / 0.05 100 / 0.005 100 / 0.01

100 / 0.05 100 / 0.005 100 / O, OO5

40 / 0.05 90/0 »0025 100 / 0.005

30 / 0.05. 100 / 0.005 100 / 0.005

O / O ₉ 05 50 / 0.05 20 / 0.05

0 / 0.1 SO / 0 ₉ 1 0 / 0.1

0 / 0.1 70 / 0.1

0 / 0.1 0 / 0.1

0 / 0.1 0 / 0.1

TSM-S

.j oMo

100 / 0.01 100 / O ₈ OOS 100 / 0.0025 100 / 0.1 100 / 0.1 100 / 0.025 10θ / θ, οο5 100/10 0/50

100/10 10/10

8o / 0.05 0/50 0/50

0 / 0.1 0 / 0.05 0/50 0/50

0 / 0.1 100 / 0.05 100/10 0/50

0 / 0.1 0 / 0.05 0/50 0/50

70 / 0.1 100 / 0.1 10O / 0 £ 25 100 / 0.05 80/50 90/50

0 / O, o25 30 / 0.1 100/0 ₉ 1 100 / 0.05 100/10 20/50

0 / 0.025 60 / 0.1 '0 / 0.025 80 / 0.01 70/50 0/50

PO

- House? Iy (housefly) PO - Plum Curculio (plum

- Mexican Bean Beetle (Safer d "Mexican bean) made)

- Pea Aphid ORW "Corn Hoot Worm (cereal] _ΜΛ ., - Southern Army Worm (southern army worm) · root maggot) H-TSM - Resistant two-spotted Mite (resistant, PA-S - Pea Aphid - Systemic

branched mite) '(pea louse - systemic)

TSM-S - T-wo-spotted Mite-Systemicl (two-spotted mite systemic)

1 Connection of
example QQQ
WWW
Ol Vyy Vyy _R 2 Tabel R ² CO
R ⁵ 4 - Insect toxicity of compounds 1
r I. co 29
30th
31 CH ₅ . CE ₅
CH ₅
CH ₅ ■ do
JB * the formula i-HjUp — O * i ν »J ± t ^ ρ
1Λ * K CM
I. 32 CH ₅ CH ₅ H
'CH ₅
H CO 33
34 C ₂ H ₅ C ₅ H ₇
CH ₅ CH ₅ C. CC '
O 35 CH ₅ H
H JL CD
CO
- ^ H
CH ₅
H CH ₅ S.
S.
O CH ₅ "O _m he·
NJ H
H O
O CH ₅ S.

CD CD CD

Table 4 (continued)

CD
O
CD
CO

Compound of Example 29 30 31 32 33 34 35

HP * / *

92/05

24/05

48/05

1.00 / 05

t00 / 05

88/05

PA

SAW

ESM

MBB * / *

30/005 100/005 100/05 10/005

100/005 80/005 100/05 40/01

100/005 100/005 0/0 _β 1 90/01

100/001 tOO / 005 70/05 60/01 100/005 100/01 100/025 90/01

100/005 100/001 90/05 100/01

CRW PA-S

TSM-S

40/025 100/005 100/01 100 / 0.1 '100 / 0.1

Note: 005 = 0.005 _f 05 = 0.05, 01 = 0.01 60/05
100/025
0/05

60/05
100/05

60 / 0t

HP

MBB

PA

SAW

TSM

PO

CRW

PA «* S

ISM-S 60/05 100/10 0/10 100/05 90/10 0/10

0 / 0.1 100/10 0/50

60/05 100/10 100/10

80/05 100/10 100/10

0/05 100/10 100/10

100/50 100/50

House Ply (housefly)

Mexican Bean Beetle

Pea ApMd (pea louse)

Southern Army .Worm

Two-spotted mite.

Plum Curculio (plum maggot)

Corn-Root Worm

Pea Aphid-Systemic (plant louse - systemic)

Two-spotted Mite-Systemic (two-spotted mite-systemic;

CD CD CD

From these data it can be seen that the inventive
Compounds for insects are selective contact poisons. It can also be seen that the compounds of Examples 1 to 21, 24 and 26 to 35 have systemic toxicity to pea louse ",

Thus, the invention provides novel and useful _e Insektioide

9 0 9 8 3 ^l o I 1 b h 7

Claims (1)

Claim " 1, Organic phosphorus compound of the formula: k ^^ ^^ N- * OH ~ SPY (OR ¹ ) ρ I I r4 _O r5 _Ce0 in which T is equal to 0 or S, A is equal to 0, S, RK or R ⁶ OOH, R ¹ is OH ₅ or O ₂ Hg, R is OH ₅ , O ₂ H ₅ or O ₅ H ₇ , and R ² , R ⁵ , ΈΓ and R ⁵ are H or OH ₅ , where in the case (1) that A is R ^ N, at least one of R and R is OH, and at least one of R ⁴ and R ^{p is} equal to H, and in the case (2) that A is equal to R ⁶ OOH, R ^{2 is} equal to H. 2 * Insectioidt mass., Characterized in that it is a Compound of the formula: 1 - ² Γ Γ r4qR ⁵ 0 * 0 R ⁶ OH-SPY (OR ¹ ) ₂ has, in which Y is the same 0 or S, A is the same 909836/15 5 2 13th 0 »S, R ³ IT or R ⁶ OON is R ¹ is OH ₅ or O ₂ Hc is _t R ⁶ is OH ₃₁ O ₃ H ₅ or O ₃ H ₇ , and R ² , R ⁵ _t R * and R ⁵ are H or OH ₃ , where in the case of CO »^ ^β JL is the same R- ⁵ H, at least one of R and Έ. equals OH ₃ , and at least one τοη R ^4- and Br equals H, and for the case (2) that A equals R ⁶ OOIf iat, R equals E is " ¥ water-dispersible mass naoh claim 2, dadureh characterized in that it has a dispersant therefor Water-dispersible mass according to claims 2 and 3, since characterized in that the dispersant is an inorganic, finely divided, surface-active Solid is * Water-dispersible mass according to Claims 2 and 3, characterized in that the dispersant is an or * Ganisches surface-active agent and the measure "has an organic solvent in which the Compound is soluble in an amount sufficient to produce a flowable solution * 6 · Method for killing insects, characterized in that the insects are treated with an effective Amount of a compound brings into contact, which is the formula R ⁴ QR 9 0 9 8 3 6/1552 in which X is equal to O or S, A is equal to O, S, E ⁵ H or R ⁶ OON »R ^{1 is} equal to OH ₅ or O ₂ Hg, R equal to OH ₃ , O ₂ H ₅ or O ₃ H ₇ , and R ² , R ⁵ , R ⁴ and R ^{5 are} equal to -HE or OH ₅ , where for the case (1) that A is equal to Έ? Ϊί , at least one of R and R is equal to OH, and at least one of R ^4- and R ^{5 is} equal to H, and in the event (2) that A is equal to R ⁶ OON, R ^{2 is} equal to H 909836/15 5 2