CS244135B2 - Method of thioglycollic acid's amides s-(dialkoxythiophosphoryl)production - Google Patents

Description

The invention relates to a process for the preparation of S-dialkonytiophosphoryl thioglycolic acid amides of the general formula I

R

R

«) · ^{K d} e ^R and ^R1 are the same or different and znenemjí eltexylovou stapinu and 1 Al 5 carbon atoms and ^{R 2} and R ^p are the same or different and znameují at ^ om hydrogen and ^lkyl verifies SKU ^p yne and ¹ * '6 ^t OMYA atoms, phenyl optionally substituted by halogen atoms or groups having ¹ alkyloiýtai ai Uhl ^C2 ^ u, ^P ^ nu yridylovou hundred, not a ^{b R2.} and ^R 'Uoří with ^p ol atom soul morpholine residue.

Said amides are known compounds and many of them are known under the protected names as Cyyon-torphooox-Elfix. Ithocron, E77, Foefotion and Delli as active pesticides and ecaricides.

Among the numerous. Processes of these compounds, which are known, include processes which involve condensation of the sodium, potassium or calcium salt of a dioxy compound. Phosphoryl Chloacactate (C. Fest and R.J. Schrnidt; Insectize 1h) xphoxuric ester Ln Chemie dor Pn.ansena.dtatz und Schadlinosbekamppfugoteittte, Vol. 1, WegOer R, Bd, Springer Verlag Brlin, 1970), or a haloacetyl hexooenidene (G. Schreder: Die Entrnieklung neuer insgkttziden ρ ‰ 8ρ> Ver ‰ Γ Γ ester ester Ver Ver Ver Verlag Chode, Weeinieim, 1963) and followed by adrolysis of the obtained ester or alternative which comprises the reaction of a carbonyl lithium thio sulphate with a salt of O, O-di-thiophosphoric acid (SCC: DLi Neutrine Phosphorsulfuttster Verlag Chemie, Leinheim 1963).

Those skilled in the art are familiar with U.S. Pat. a process consisting in the condensation reaction of di-oxylsilyl phosphorus salts with elpha, beta-cyenoalkylamides of hgloggnic acid

All of the above known methods for the preparation of thixolic acid amides are multi-step procedures and require difficult to obtain materials. Certain problems also occur in operations associated with the separation of the product from the mixture. The yields of these processes are between 65 and 95% based on the last stage of the synthesis.

Process for the preparation of ammonium salts of 18-oxo-oxoacrylic acids of general formula I

wherein R and R ¹ are the same with different mean Neto aJ.koxy ^ hydrocarbyl of ^{1 and 5} - ^with carbon atoms and R ² and R are the same or different and hydrogen, and znaιniníjí ^ tkylovou group with the phenyl group optionally substituted by halogen or C ^ g alkyl, pyrfdylovou group, or R and R together with the nitrogen atom form a radical mooďolinu- .spočívá- the present invention by reacting a bromide of S- ^ ill ^{χyt t} x of ^{NO χ} oofox У ^t IX ^on lУkolxv ^sic ^ eHny of formula II

(Π) (III) where ^R β й has the above-mentioned exclusion, and aulne of general formula III

R ²

HN ^ ^ й ³

Wherein R * and R * solder as defined above, optionally in the presence of a tertiary amine of formula IV

(iv) л e of:

^kd e R \ e ^{g6 R5} are the same and different Neto znameenaí alkyl with u ^{to p} yne with 1-6 carbon atoms or erylovou group, in an aprotic solvent at a temperature of from -20 to • the fifth ° C, preferably from -3 to 5 ° C.

As aprotic solvents, it is preferred to use benzene, hexane, chloroform, carbon tetrachloride, ethyl ether of the mixture of said solvents.

The process for producing the amides of the invention is a simple and highly efficient process. K ¹ mol of perfluorooctyl bromide S- ^ ^b ^ Sielko tiofosfoi ^ iJ U.ogtykolové acid. to use ^and · to ² moles of amine of ^b Proceed with ^h of Formula HI ^kd e ^{R 2} and ^R maai above uvefoný meaning pMčtmž ^- in at ≤ e, ^z e using 1 mole of amine, - the process is performed in přítomnati 1 mole of tertiary amine of formula IV, ^w e ^R \ ^R5 and ^R6 as defined above eat.

The process of the present invention yields readily said compounds, the process may be carried out in a single reaction vessel without isolation of the freshly prepared reactant of formula (II), which is a novel compound and is prepared by reaction of thioxophene. The synthesis of t1 (1880orano8ulfmyyl) is disclosed in Polish Patent Specification No. 127,744.

Isolation and purification of the product is accomplished by distillation under reduced pressure or by taryalization

The yields of the amides prepared according to the process of the present invention are in the range of 95 to 98% based on the thioxophosphatosulfuramide from which the starting material of the formula II is obtained.

The purity was determined to základš analysis of the reaction mixture after ukonSenK resonance technique ⁽ⁱⁿ ° ltřn ^s Starn aM ^ 85 * and elemental analysis were mined složčamim ^y

It is 98 to 99%. The amides obtained by the process of the invention can be used as pesticides directly in the raw state, without purification.

The following examples illustrate the process of the invention without limiting it in any way.

He did

To a solution of 24.7 g (0.1 mol) of bromo-2,2-dihydroxybromide-thioglycolic acid bromide in 150 ml of benzene was added dropwise 18 ml. , 6 g. (* 0.2 mol). of aniline in 25 ml of benzene at +3 ° C. The mixture is left at 20 DEG C. for 35 minutes, the aniline hydrobromide is filtered off, and the solvent is removed under reduced pressure (0.6 kPa). Ztytek was crystallized from n-hexane to give 25.4 g flux (98 *) of 2,2-bis- aniliež eimetylpropoxyУtofoaforyL thioglycollic acid ³ mr P j pprn +92.4 '(St ₂ O) (H ^ ert .).

For

244135 4 calculated 53.68 XC - 7.5 X H 3.4 X M 7.6 X P nelezeno 53.5 »C 7.4 X H 3.6 X N 8,7 X P. Example 2. ¹ A solution of 33.75 g (0.15 mol) of freshly prepared S- / cis-bromo-bromo / thio-bromo / thio bromide

glycol thyeelines ^ν · 200 ml of carbon tetrachloride is saturated from stirring at -3 ° C with ammonia gas, - until the reaction ceases to be exothermic.

Stirring is continued for 15 minutes at 15 ° C, then 100 ml of water are added. The organic layer was separated, dried with magnesium sulphate, the solvent was distilled off under reduced pressure (50 mm Hg) and the residue was recxyytalized from 1: 1 benzene-peerol ether to give 11.9 g (91%). (S- (trans-propylmethylsulfonyl)) thioglycol thalliamide, m.p. 65 ° C.

³ * ^P at ⁺⁹⁰ ppm ⁽ CCl ^) (Н ^ ГО ^ ext.).

Proche _1T NO ₃ PSG

calculated 35.4 X C 6.6 X H 5.1 X N 11 , 4 X P nelezeno 35,6 XC 6.8 X H 5.0 X N 1 , 5 X P. Example 1. p d 3 Solution 17.4 g (0.2 mol) besvodího morpholine ve 100 ml of benzene is added dropwise at the temperature of

The mixture was stirred at +5 ° C for freshly prepared S-dimetho-sophio-thio-iso-yoyl) -glycolic acid bromide (27.9 g, 0.1 mol) dissolved in 50 mL hexane. Remove the solvent from the reduced pressure (20 ° C, 0,20.2 kPs) and add 20 ml of water and 100 ml of chloroform to the residue. The solid layer was separated, washed twice with 15 ml of water and dried over magnesium sulfate. After filtering off the drying agent and rddeetilování solvent gave 26.5 g (93 X), S-moofolidu 0imetoxytiofooooiy y thioglycollic acid as olejovUá Kepala-y after curing ochlezo-, melting point 59 EŽ 63 ° C, ³¹ P ^ + 97.7 IRU ^pp m (CC1 _4).

For 0θΗ ₁₆ Ν0 ₄ Ρ3 ₂

calculated 33.7 X C 5.6 X H 4.9 X M 10,8 X P nelezeno 33.0 X C 5.6 X H 4.9 X N 11.4 XP. ’ N ^ -example 4 K-solution 22.5 g (0.1 mol) of the same as in Example 2 in 100 ml of dichloroethene

10.1 g (0.1 mol) of triethylamine and 9.4 g (0.1 mol) of 2-aminopyridine dissolved in 50 ml of benzene are slowly added at -15 ° C. Strong —cMní. It is then stirred at + 15 ° C and the solution is sent at + 10 ° C under reduced pressure of 0.6 kPa. The syrupy residue is dissolved in 100 ml of chloroform and treated twice with 25 ml of water. The organic layer was dried over sodium sulfate, redissolved and the solvent was evaporated, yielding 33.7 g (97%) of 3-isopropyl-2-pyrrolidin-2-yl-thioglycolic acid lipid 2-pyridyl as yellow. oily liquid ^- ,, ³¹ P rn-J '+87.8' ppa. (CH2Cl2).

For Cf jjjjNOO ^ ^Pg *.

calculated 44.8 X C 6.0 X H 8.0% H- 8.8 X P found 44.7 X 0 6.4 X H 8.2 X Mi 9.0 X P.

Example 5 _t ·

31 g of a 20% ether solution of methylartn was added dropwise to the freshly prepared bromo same as in Example 3 (27.9 g of 0.1 mol) in 100 ml of benzene under stirring at 0 ° C.

The methylamine hydrobromide is filtered off, the solvent is removed at + 10 ° C under a reduced pressure of 665 Pa and the residue is distilled. There were obtained 35.0 g (97% aetylaaidu S ·'dimetoxy tiofosforyl thioglycollic acid C, ³¹ P .M-and ^{4+ 98} 1 ppn (H1 _4).

^{4 + 9} boiling point

105-107 1.3 Pa, m.p.

For C ^^ PS ² requires started up

26.2% C

26.1% C

5.2%

5J%

6.6

13.5 »P 13.8% P.

(Mcl · mol) of the same bromide as in Example-3

To a freshly prepared solution of 27.9 g (0.1 in 100 ml of carbon tetrachloride), 14.6 g (0.2 mol) of diethyl amine in 15 ml of ethyl ether are added dropwise with stirring at 0 DEG to 3 DEG C. The reaction mixture is left for 45 minutes. 50 ml of water are added at + 20 ° C.

OrgaMcká odděěí layer, dried over <m sulphate, filtered and after removing the solvent (20 ° C, 1.33 W ^ ed ^ afforded 28.9 (98%) of S- dimeetoxytofosforyl diethylamide - thio ^Gly ko ^l ^ ew зсИп ^ ^{3 'P} ° MRJ 98.6 ppm (CC1 _4).

For C ^^ PS ² Calculated Found

35.6

34.7

6.64%

6.5%

5.16% H

6.3% N

11.4% P

11.6% P,

Example (K ² «H ^and R ³ «

-C (CH3CP))

To the solution

27.2 g (0.075 mol) of S-diisobutoaxthiophthiophyl thiogtycolic acid bromide dissolved in 100 ml of benzene are added in a mixture of 8.02 g (0.075 mol) of 4-methylenine a. 7.6 g (0.075 moo) of triethylamine in 80 ml of benzene at 5 ° C. the mixture is left at 20 ° C for minutes, then 70 ml of water are added. The benzene layer was separated and screened with magnesium sulfate. The desiccant was filtered off and the solvent was evaporated. Ae give 28. ^(96%) of ^4-n meeylan l u ^{id S} - 'dilsobutO thio ^ ^ S ^ engraved (CC1 _4).

₃ i V- ^g thio ^g l ^y wheeled ^{3> P} mj ^j Γ88 ^{, 9} ppa '

Pro'C17H20NO3PS ²

calculated 52.4% C 7.2% H 3.6% N 7.9 »P nelezeno 51.7 % C 7.1% H 3.35% K 8.12% P Example 8 (R ² = H e R ³ C) ^ BríP))

To the solution

27.2 g (0.075 mole) of S-di-4-oxo-butox-1-ylphosphoryl-thioglycolic acid bromide dissolved in 100 ml of benzene - a solution of 12.9 g is added dropwise by stirring at 0 to 5 ° C. (0.075 mol) 4-bromoballine and 7.6 g (0.075 mol) triethylamine in 100 [mu] l benzene. After completion of the dropwise addition, stirring was continued for 30 minutes at 20 ° C and 50 ^% water was added. The organic layer was separated and dried with magnesium sulfate. The desiccant was filtered off and the solvent was evaporated (20 ° C and 1.33 kPa).

ská

To afford 32.6 g (96 56- 4 bromen01idu S- diisobutoiqrtiofosforyl thioglycollic tyaaHáy, ³¹ P ^y IRU 87.6 ppm (CC1 _4).

For C | 6H25 3P ^NO 2 ^{Br S} Calcd started up

42.3

41.7

5.5% H

5.3% H

3.08

3.3

6.8%

6.5 «

P P <

Claims (2)

SUBJECT NAL A process for producing amides S-dialkoxythiophosphoryl thioglycolic acid of formula I (I). where ^R a. ^{r 1} are the same or different and denote an ethoxy group of β 1 to 5 carbon atoms, and R ² and r ³ are the same or different and are each a hydrogen atom, an allyl group having ¹ to 5 carbon atoms; 6 carbon atoms, phenyl optionally substituted by halogen atoms or alkyl \ ýtai skuptaami and ^{1 and} 2 carbon-11 wrid ^^ ^ ^ verifies with no ^pin-b of ^R2 and ^R3 together with the nitrogen atrocm ztytek morpholine, characterized in! by reacting the bromo-S-dialkoxrtiophosphoryl thioglycol thiamyl-II of the formula II (II), wherein R β ^r 1 is as defined above, with an amine of the formula ¹¹¹ (III), 2 3 R and R 'owner abovementioned meaning, if appropriate in tertiary přítomooti ariLnu general formula IV (IV) wherein ^R \ and ^R & ^R5 are stance or differences and znameenaí alkyl.ovou' group, and a ^{is from 1 to 6} carbon atoms, or an aryl group, in an aprotic solvent environment at a temperature of about 10%. from -20 to 15 ° C, preferably from -3 to .. -5 ° C. 1 2. The process of claim 1 wherein the eprotic solvent is benzene, hexane, chloroform, magnesium chloride, ethyl ether, or mixtures of said solvents.