US3816456A - (di)-thiophosphonic acid esters,(di)-thiophosphonic and-phosphoric acid ester amides - Google Patents

(di)-thiophosphonic acid esters,(di)-thiophosphonic and-phosphoric acid ester amides Download PDF

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US3816456A
US3816456A US00293132A US29313272A US3816456A US 3816456 A US3816456 A US 3816456A US 00293132 A US00293132 A US 00293132A US 29313272 A US29313272 A US 29313272A US 3816456 A US3816456 A US 3816456A
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thiophosphonic
carbon atoms
formula
alkyl
acid esters
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US00293132A
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G Hoerlein
G Salbeck
L Emmel
W Bonin
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Hoechst AG
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Hoechst AG
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
    • C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
    • C07F9/657154—Cyclic esteramides of oxyacids of phosphorus

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  • DD-THIOPHOSPHONIC ACID ESTERS (DD-THIG- PHOSPHONIC AND -PHOSPHORIC ACID ESTER AMIDES Gerhard Hiirlein, Frankfurt am Main, Gerhard Salheck, Kelkheim, Taunus, Ludwig Emmel, Bergen-Enkheim, and Werner Bonin, Kelkheim, Taunus, Germany, assignors to Farbwerke Hoechst Aktiengesellschaft vormals Meister Lucius & Bruning, Frankfurt am Main,
  • R is alkoxy having from 1 to 6 carbon atoms if R is alkyl or phenyl, amino, alkylamino or dialkylamino each having from 1 to 6 carbon atoms, or alkenylamino having from 1 to 4 carbon atoms;
  • R is hydrogen or alkyl having from 1 to 4 carbon atoms
  • R is hydrogen, alkyl having from 1 to 4 carbon atoms
  • X is oxygen or sulfur
  • the present invention relates to novel 4-thiochromanyl- (di)-thiphosphonic acid esters, 4 thiochromany1-(di)- thiophosphonic acid esters, 4 thiochromanyl (di)-thiophosphonic and -phosphoric acid ester amides of the formula where R; is alkyl or alkoxy each having from 1 to 4 carbon atoms or phenyl;
  • R is alkoxy having from 1 to 6 carbon atoms if R is alkyl or phenyl, amino, alkylamino or dialkylamino each having from 1 to 6 carbon atoms, or alkenylamino having from 3 to 6 carbon atoms;
  • R is hydrogen or alkyl having from 1 to 4- carbon atoms
  • R is hydrogen, alkyl having from 1 to 4 carbon atoms
  • X is oxygen or sulfur
  • novel compounds have excellent insecticidal, acaricidal and nematocidal properties.
  • R methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl,
  • R methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, secondary butoxy, tertiary butoxy, R
  • R is alkyl having from 1 to 4 carbon atoms and R is alkoxy having from 1 to 4 carbon atoms, or R is alkoxy having from 1 to 4 carbon atoms and R is amino, alkylamino or dialkylamino having each from 1 to 3 carbon atoms or allylamino.
  • R and R are:
  • the phosphorus compounds of formula III react easily with the 4-halogeno-thiochromanes of formula II, at temperatures in the range of from 0 to 120 (1., preferably from 10 to C. It is recommended to operate in the presence of a solvent or diluent inert to the reactants, especially lower aliphatic ketones, such as acetone or methylethylketone; alkanols, such as methanol, ethanol or isopropanol; esters, such as acetic acid ethyl ester; nitriles; N-alkylated acid amides, such as dimethylformamide; ethers, such as dioxan, glycol-dimethyl ether or tetrahydrofuran; aromatic hydrocarbons, such as benzene or toluene; halogenated hydrocarbons, such as chloroform or carbon tetrachloride, and water, as well as mixtures of such solvents with water.
  • the reaction proceeds with exchange of the halogen atom of formula II. Therefore, it is carried out either with addition of acid binding agents, or using salts, especially alkali metal or ammonium salts of the phosphorus compounds of formula III.
  • acid binding agents are alkali metal hydroxides and alkali metal carbonates; but tertiary nitrogen bases, for example pyridine or triethylamine, may also be employed.
  • the starting compounds of formula III are known and can be easily prepared according to usual methods.
  • EXAMPLE 40 Horse beans (Vicia faba) heavily infested with bean aphids (Doralis fabae) were sprayed, until beginning dripoff, with the aqueous dilution of an emulsifiable concentrate containing 0.000375 weight percent of the compound of Example 3. The sprayed plants were then placed at 20 C. in a greenhouse; evaluation was carried out 24 hours after spraying. All aphids were killed.
  • EXAMPLE 41 Young cotton plants (Gossypium spec.) in pots, infested with African cotton strainers (Dysdercus fasciatus), were sprayed, until drip-off, with the aqueous dilution of a wettable powder concentrate containing 0.006 weight percent of the compound of Example 23. Subsequently, the plants containing the bugs were put into cylindrical gauze cages and placed in a greenhouse at 20 C. A cntrol after 48 hours showed that all cotton stainers were killed.
  • EXAMPLE 42 Larvae (4th stage) of the Mexican bean beetle (Epi- Iachna varivestis) and leaves of the dwarf-bush bean (Phaseolus vulgarz's) were sprayed, by means of a spraying apparatus, with a dosed amount (corresponding to an application amount of 600 liters of spray liquor/ha. in the open fields) of the aqueous dilution of an emulsifiable concentrate containing the preparation of Example in a concentration of 0.002 weight percent.
  • the leaves and beetle larvae were placed in open vessels at 22 C.
  • the control 47 hours after spraying proved that all larvae were killed.
  • tions was determined by evaluating the inhibition of oviposition expressed in percent; 100% inhibition meaning that all ticks treated with one active substance concentration did not oviposit, 0% meaning that all ticks did oviposit.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
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  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

COMPOUNDS OF THE FORMULA

4-(R1-P(=X)(-R2)-S-),R3,R4-THIOCHROMAN

WHERE R1 IS ALKYL OR ALKOXY EACH HAVING FROM 1 TO 4 CARBON ATOMS OR PHENYL; R2 IS ALKOXY HAVING FROM 1 TO 6 CARBON ATOMS IF R1 IS ALKYL OR PHENYL, AMINO, ALKYLAMINO OR DIALKYLAMINO EACH HAVING FROM 1 TO 6 CARBON ATOMS, OR ALKENYLAMINO HAVING FROM 1 TO 4 CARBON ATOMS; R3 IS HYDROGEN OR ALKYL HAVING FROM 1 TO 4 CARBON ATOMS; R4 IS HYDROGEN, ALKYL HAVING HAVING FROM 1 TO 4 CARBON ATOMS; OR HALOGEN; X IS OXYGEN OR SULFUR; ARE USEFUL PESTICIDES IN THE AGRICULTURAL AND VETERINARY FIELDS.

Description

United States Patent (DD-THIOPHOSPHONIC ACID ESTERS, (DD-THIG- PHOSPHONIC AND -PHOSPHORIC ACID ESTER AMIDES Gerhard Hiirlein, Frankfurt am Main, Gerhard Salheck, Kelkheim, Taunus, Ludwig Emmel, Bergen-Enkheim, and Werner Bonin, Kelkheim, Taunus, Germany, assignors to Farbwerke Hoechst Aktiengesellschaft vormals Meister Lucius & Bruning, Frankfurt am Main,
rmany No Drawing. Filed Sept. 28, 1972, Ser. No. 293,132 Claims priority, application Germany, July 22, 1972, P 22 36 118.8 Int. Cl. C07d 65/08 US. Cl. 260-327 TH 9 Claims ABSTRACT OF THE DISCLOSURE Compounds of the formula where R; is alkyl or alkoxy each having from 1 to 4 carbon atoms or phenyl;
R is alkoxy having from 1 to 6 carbon atoms if R is alkyl or phenyl, amino, alkylamino or dialkylamino each having from 1 to 6 carbon atoms, or alkenylamino having from 1 to 4 carbon atoms;
R is hydrogen or alkyl having from 1 to 4 carbon atoms;
R, is hydrogen, alkyl having from 1 to 4 carbon atoms,
or halogen;
X is oxygen or sulfur;
are useful pesticides in the agricultural and veterinary fields.
The present invention relates to novel 4-thiochromanyl- (di)-thiphosphonic acid esters, 4 thiochromany1-(di)- thiophosphonic acid esters, 4 thiochromanyl (di)-thiophosphonic and -phosphoric acid ester amides of the formula where R; is alkyl or alkoxy each having from 1 to 4 carbon atoms or phenyl;
R; is alkoxy having from 1 to 6 carbon atoms if R is alkyl or phenyl, amino, alkylamino or dialkylamino each having from 1 to 6 carbon atoms, or alkenylamino having from 3 to 6 carbon atoms;
R is hydrogen or alkyl having from 1 to 4- carbon atoms;
R, is hydrogen, alkyl having from 1 to 4 carbon atoms,
or halogen;
X is oxygen or sulfur;
with the proviso that R and R cannot both be alkoxy.
The novel compounds have excellent insecticidal, acaricidal and nematocidal properties.
3,816,456 Patented June 11, 1974 "ice As substituents, the following radicals may for example be cited:
R =methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl,
secondary bntyl, tertiary butyl, phenyl; R R =methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, secondary butoxy, tertiary butoxy, R
Preferably used are those (di)-thiophosphonic acid esters and (di)-thiophosphoric acid ester amides in which R, is alkyl having from 1 to 4 carbon atoms and R is alkoxy having from 1 to 4 carbon atoms, or R is alkoxy having from 1 to 4 carbon atoms and R is amino, alkylamino or dialkylamino having each from 1 to 3 carbon atoms or allylamino. Preferred radicals R and R are:
R =hydrogen, methyl, ethyl; R =hydrogen; fluorine, chlorine or bromine in 6- or 7- position.
For the preparation of the compounds of formula I, 4- halogeno-thiochromanyl compounds of the formula Hal R4 where Hal is halogen, especialy chlorine or bromine, are reacted with phosphorus compounds of the formula P-SH Pea ii 111 or salts of such phosphorus compounds, if necessary in the presence of an acid binding agent.
The phosphorus compounds of formula III react easily with the 4-halogeno-thiochromanes of formula II, at temperatures in the range of from 0 to 120 (1., preferably from 10 to C. It is recommended to operate in the presence of a solvent or diluent inert to the reactants, especially lower aliphatic ketones, such as acetone or methylethylketone; alkanols, such as methanol, ethanol or isopropanol; esters, such as acetic acid ethyl ester; nitriles; N-alkylated acid amides, such as dimethylformamide; ethers, such as dioxan, glycol-dimethyl ether or tetrahydrofuran; aromatic hydrocarbons, such as benzene or toluene; halogenated hydrocarbons, such as chloroform or carbon tetrachloride, and water, as well as mixtures of such solvents with water.
The reaction proceeds with exchange of the halogen atom of formula II. Therefore, it is carried out either with addition of acid binding agents, or using salts, especially alkali metal or ammonium salts of the phosphorus compounds of formula III. Preferred acid binding agents are alkali metal hydroxides and alkali metal carbonates; but tertiary nitrogen bases, for example pyridine or triethylamine, may also be employed.
The starting compounds of formula H and their preparation are described partly in French Patent Specification No. 1,584,755, partly in copending application Ser. No. 293,134 filed concurrently herewith.
The starting compounds of formula III are known and can be easily prepared according to usual methods.
The compounds of formula I are suitable for the destruction of numerous pests in crop plants including their 0 2 a 8 md H21: pd 8 .....n.....n.n.n."4:354=0: wdm 9w a 19 3 N6 .22.... c6 bdw E do v 2 a mi 93 v... ad .21 w 3 1.62.... 284 na m0 0 mm m I 5M2 6 H. Ow m .w m cdm Q6 Q6 ads a in u. we .1... 343 m o m .1 mm E50 16 m fl 0 3 Tm v 2 1m .2 2 A: 5 0 O 5 100 16 m w v V 9mm w c S 1.. om .........NH3.H m O m 3 m m 2 m h 6 O m N Z m .m 6 O cwwwbo 60 L -53 9535 .6 a: EEQ QEEE E 331630 e? 3 528 $5955 mafia; m;
n \Q m 2.1.1-.. 1.-.... 2 ma ca .:...5...}...:.....:....... am 333%: 550 0 mm 6 momz l6. 1 mu. 0 8 2 w: m mfa Eoo o a m 2 A52 16 m m \n Er nu ma 9: 3 w z 2 3 a nf E60 0 8 v 0 m/ 4 6 mo m 1 w 6 0 0 awo mz 3. \fl v E :5. .ww w 0 2 w 8. &8 56 0 o 28 m twfimz 1w m \m 3. 3: g 3 2 a -335 52 2 E60. 0 E 5 1 w/ mo m EM m2 1% \fi 3: 2 3 m2 2 3 mm 560 o 2 m m z m m 6 o m m z m m 6 0 Wm? 0 0v 5 5: S PH 2 5 M 2 PM US$ 30 5 8 E088 @5895 29254 32 1 7 EXAMPLE 39 Young apple trees planted in pots and heavily infested with a phosphoric ester resistant strain of the European red mite (Metaterranychus ulmi) were sprayed, until beginning drip-off with the aqueous dilution of an emulsifiable concentrate containing 0.003 weight percent of the compound of Example 13, and subsequently placed in a greenhouse at 20 C.
A microscopic control after 8 days showed that all mobile and immobile stages were killed.
The following commercial phosphoric acid esters used in comparative tests showed no activity even at higher concentration phenkapton, 0.025 weight percent, no effect demeton-Smethyl, 0.05 weight percent, no effect dimethoate, 0.05 weight percent, no effect.
Tested in the same manner, the compounds of Examples l, 9, 15, 17, 19, 28 and 33 proved to be of equal activity.
EXAMPLE 40 Horse beans (Vicia faba) heavily infested with bean aphids (Doralis fabae) were sprayed, until beginning dripoff, with the aqueous dilution of an emulsifiable concentrate containing 0.000375 weight percent of the compound of Example 3. The sprayed plants were then placed at 20 C. in a greenhouse; evaluation was carried out 24 hours after spraying. All aphids were killed.
Tested in the same manner, the compounds of Examples 1, 2, 8, 10, 13, 15, 23, 25 and 30 showed equal ac tivity.
EXAMPLE 41 Young cotton plants (Gossypium spec.) in pots, infested with African cotton strainers (Dysdercus fasciatus), were sprayed, until drip-off, with the aqueous dilution of a wettable powder concentrate containing 0.006 weight percent of the compound of Example 23. Subsequently, the plants containing the bugs were put into cylindrical gauze cages and placed in a greenhouse at 20 C. A cntrol after 48 hours showed that all cotton stainers were killed.
Tested in the same manner, the compounds of Exam pics 1, 3, 28 and 33 showed the same good activity. The following phosphoric acid esters tested comparatively showed activity only at a considerably higher concentration:
Lethal concentr.
Diazinone 0.025% of AS Dimethoate 0.025% of AS Azinphos-ethyl 0.05% of AS No'rn: Aszactive substance. weight percent.
EXAMPLE 42 Larvae (4th stage) of the Mexican bean beetle (Epi- Iachna varivestis) and leaves of the dwarf-bush bean (Phaseolus vulgarz's) were sprayed, by means of a spraying apparatus, with a dosed amount (corresponding to an application amount of 600 liters of spray liquor/ha. in the open fields) of the aqueous dilution of an emulsifiable concentrate containing the preparation of Example in a concentration of 0.002 weight percent. The leaves and beetle larvae were placed in open vessels at 22 C. The control 47 hours after spraying proved that all larvae were killed.
Tested in the same manner, the compounds of Examples l, 3, 15, 17, 21, 23 and 25 had equal activity.
EXAMPLE 43 In vitro test on ticks of the Boophilus species (1) Boophilus microplus (a) strain of normal sensitivity (b) Biarra strain, resistant (c) Mackay strain, resistant (2) Boophilus decolora tus, resistant strain For the preparation of a suitable formulation, 10 parts by weight of active substance were dissolved in 100 parts by volume of a mixture of cyclohexanone and nonylphenol (10 E0, 8:1), and the emulsifiable concentrate so obtained was diluted with water to attain the desired concentration.
10 adult female ticks of the cited species and different sensitivity to phosphoric esters, which had sucked themselves full of blood, were dipped for 5 minutes into these dilutions. Subsequently, the ticks were sticked with their dorsal side onto an adhesive tape and kept in a Warming closet (28 C., about of relative air moisture) for oviposition.
Two weeks after treatment the activity of the formula: tions was determined by evaluating the inhibition of oviposition expressed in percent; 100% inhibition meaning that all ticks treated with one active substance concentration did not oviposit, 0% meaning that all ticks did oviposit.
TABLE IL-IN VIIRO TEST ON 'JIICKS OF DIFFERENT PHOSPHORIC ESTER SENSITIVITY Inhibition of oviposition in percent Boophilua mtcroplua Concen- Buophilua tration Strain of Bizarre Mnckay decolof active normal strain strain oratus substance senslresist- (resist- (resist- Exemple in percent tivity ant) ant) ant) We claim:
1. A compound selected from the group consisting of 4-thiochromanyl-(di)-thiophosphonic acid esters, 4-thiochromanyl-(di)-thiophosphonic and -phosphoric acid ester amides of the formula where 2. The compound of the formula 8 CH: s l
3. The compound of the formula B 8-K 001R! 4. The compound of the formula 8 84 :i OCzHa F 5. The compound of the formula 6. The compound of the formula S CH 7. The compound of the formula ISI/OH: 5-1
8. The compound of the formula s 01H; s l C1 ocgHl 9. The compound of the formula 0 CH: s-l
NC 01 a):
References Cited UNITED STATES PATENTS 11/1966 Kilsheimer et a1. 260-830 5 2/1969 Melton et a1. 260-3305 6/1971 Barker 260+-327 1/ 1973 Boissier et a1. 26O32'7' HENRY R. JILES, Primary Examiner C. M. S. J AISLE, Assistant Examiner US. Cl. X.R.
US00293132A 1972-07-22 1972-09-28 (di)-thiophosphonic acid esters,(di)-thiophosphonic and-phosphoric acid ester amides Expired - Lifetime US3816456A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3948945A (en) * 1973-08-14 1976-04-06 Hoechst Aktiengesellschaft 5-Homothiochromanyl-(di)-phosphoric (-phosphonic) acid esters

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3948945A (en) * 1973-08-14 1976-04-06 Hoechst Aktiengesellschaft 5-Homothiochromanyl-(di)-phosphoric (-phosphonic) acid esters

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DE2236118B2 (en) 1976-05-06

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