The method of obtaining s-dialkyl, alkylphenyl or diphenylarsinic esters of 4-methoxyphenylacetone acids


C07F9/74 - Aromatic compounds
C07F9/72 - Aliphatic compounds

 

(57) Abstract:

Use in chemistry postranecky compounds. Getting S-dialkyl-, alkylphenyl and diphenylarsinic esters of 4-methoxyphenylacetone acids of the formula I, where AG-4-MeOC6H4; R is lower alkyl, phenyl; R1-ethyl, phenyl, lead the interaction of 2,4-bis-(4-methoxyphenyl)-2,4-dicicco-1,3,25, 45-dithiadiphosphetane with alkylamino or phenyl esters of dialkyl-, alkyl-, phenyl - or diphenylarsinic acid of the formula ROAsR1R", where R, R1and R" is indicated above, the 20oC in the presence or without solvent (benzene), followed by separation of the target products by the known methods (benzene). The structure of formula I:

< / BR>
The method is simple and easy to use, allows to obtain pure desired products in high yields.

The invention relates to the chemistry of organophosphorus compounds, namely to a new method of obtaining S-dialkyl-, alkylphenyl and diphenylarsinic esters of 4-methoxyphenylacetone acids of General formula I

< / BR>
where

Ar = 4-MeOC6H4;

R is lower alkyl, phenyl;

R' and R ' = lower alkyl, phenyl.

Triamcinolone and Staniloae analogues of the proposed S-dialkyl-, alkylphenyl and diphenylarsinic drugs and can also find use as intermediates for the targeted synthesis of analogues of such insecticide, as parathion, leibold, time, metasystox (U.S. Patent N 3992425 (1976). The invention abroad, 1977, vol. 4, N-6; U.S. Patent N 4588114, Rehim., 1987, P; Shrader, New organophosphorus insecticides. M.: Mir, 1965, - 488 S.).

Declare us S-dialkyl-, alkylphenyl and diphenylarsinic esters of 4-methoxyphenylacetone acid is not described in the chemical and patent literature. The inventive method has no prototypes.

The objective of the invention is to create a new way of getting S-dialkyl-, alkylphenyl and diphenylarsinic esters of 4-methoxyphenylacetone acids with good yields and high purity products.

The task was solved by the described method of obtaining S-dialkyl-, alkylphenyl and diphenylarsinic esters of 4-methoxyphenylacetone acids, which consists in the fact that 2,4-bis(4-methoxyphenyl)-2,4 - dicicco-1,3,25, 45-dithiadiphosphetane subjected to interaction with michalkaronski compounds, which are used methyl, ethyl and phenyl ethers diethyl-, ethylphenyl and diphenylarsinic acid, at 20o

The reaction proceeds according to the following scheme:

< / BR>
where

Ar = 4MeOC6H4;

R is lower alkyl, phenyl;

R' is lower alkyl, phenyl;

R" is lower alkyl, phenyl.

The structure of the obtained compounds is confirmed by IR, NMR1H and31P spectroscopy, mass spectrometry and elemental analysis. The target products in the crude reaction mixtures are formed with outputs 71-80%. The products are purified by distillation allocated to the outputs of 43-50%. The invention is illustrated by the following examples.

Example 1. S-Diethylamine-O-phenyl-4-methoxyphenylacetic-phosphonate (1).

To 3.4 g (15.0 mmol) of phenyl ether diethylaminoethoxy acid at 20oC under stirring add portions of 3.0 g (7.4 mmol) of 2,4-bis-(4-methoxyphenyl)-2,4-dicicco-1,3,25, 45- dithiadiphosphetane. The mixture is stirred for 5 h at 20oC. Distillation of the reaction mixture on the device for molecular-film distillation allot of 5.1 g (80%) S-diethylamine-O-phenyl-4-methoxyphenylacetate (1) when the temperature of thermocouple 100oC (0.03 mm RT.cent.), n2D01,6212.

An NMR spectrum31P (Bruker CXP-100, 36.5 MHz, C6H6,p, M. D.): 97.0. Range PMR (Varian T-60, 60 MHz, C6D6internal SUP>3
JNN7.0); 3.15 in (s, 3H, CH3O); 6.57 (doctor d, 2H, 3,5-H2C6H2, 3JNN9.0,4Jp-n3.5); 6.70-7.80 (m, 5H, C6H5); 8.03 (doctor d, 2H, 2,6-H2C6H2,3Jn-n9.0,3Jp-n13.0). IR-spectrum (Fourier transform infrared spectrometer Bruker IFS 113, the liquid film , cm-1): 3070 O. SL, 3042 O. SL (=C-H, Ar); 2961 Wed, 2930 Wed, 2910 sq, 2869 Wed, 2855 CL (CH3as, s), (CH2as, s); 1595 O. SL, 1500 (C=C, Ar); 1260 c , (CH2); 1025 cf /(P) C/; 830 Wed, 812 cf /P-O-(C)/; 689 O. C. (P=S), (PS2as); 565 Wed, 529 cf (P-S), (PS2s); 473 CL (As-C); 391 cf (As-S).

Found, %: C, 47.23; H, 5.30; As 17,88; P 7.06; S 15,41.

C17H22AsO2PS2.

Calculated, %: C, 47.66; H, 5.19; As 17,50; P 7.23; S 14,93.

Example 2. S-Ethylvanillin-O-ethyl-4-methoxyphenylacetone (2).

To 2.4 g (10.6 mmol) of ethyl ether ethylvinylacetate acid at 20oC under stirring add portions of 2.2 g (5.4 mmol) of 2,4-bis-(4-methoxyphenyl)-2,4-dicicco-1,3,25, 45- dithiadiphosphetane. The mixture is stirred for 2 h at 20oC, vacuum 2 h at 0.03 mm RT.article when 40-50oC. the balance on the device for molecular-film distillation allocated 2.0 g (43%) S-ethylvanillin-O-ethyl-4-methoxyphenylacetate (2) when the temperature of thermocouple 120oC (0.05 mm RT.article 6.7. Range PMR (Varian T-60, 60 MHz, C6D6internal standard (Me3Si)2O , M. D., J, Hz): or 0.83 (t, 3H, CH3CH2O,3Jn-n, 7.0); of 0.95 (t, 3H, CH3CH2As,3Jn-n u7.0); 1,51-to 1.98 (m, 2H, CH3CH2As), to 3.02 (s, 3H, CH3O); 3.67-4.17 (m, 2H, CH3CH2OP); 6.47 (D. D. 2H, 3,5-H2C6H2,3Jn-n9.0,4Jp-n3.0); 6.74-7.30 (m, 5H, C6H5+ C6H6-6); 7.91 (doctor d, 2H, 2,6-H2C6H2,3Jn-n9.0,3Jp-n14.0). IR-spectrum (Fourier transform infrared spectrometer Bruker IFS-113v, liquid film , cm-1): 3053 SL (=C-H, Ar, 2963 c, 2863 Wed, 2867 cf (CH3as, s), (CH3as, s); 1594 SR 1500 SR (C=C, Ar); 1258 Wed , (CH2); 1023 cf /(P)O-C/ a; 830 Wed, 802 cf /P-O(C)/; 691 cf (P=S), (PS2as); 577 Wed, 555 sq, 531 cf (P-S), (PS2s); 486 cf (As-C); 385 sq, 377 Wed, 360 cf (As-S).

Found, %: C, 47.29; H, 4.98; As 17.92; P 7.31; S 15.22.

C17H22AsO2PS2.

Calculated, %: C, 47.66; H, 5.19; As 17,50; P 7.23; S 14,94.

Example 3. S-Diphenylarsinic-O-methyl-4-methoxyphenylacetate (3).

To a solution of 6.7 g (from 25.8 mmol) of methyl ether diphenylarsinic acid at 20oC under stirring add portions of 5.2 g (12.9 mmol) of 2,4-bis-(4-methoxyphenyl)-2,4-dicicco-1,3,25- the 45- dithiadiphosphetane. The mixture is PE is) nepereshagnuli S-diphenylarsinic-O-methyl-4-methoxy - phenyldichlorophosphine (3).

Found, %: C, 52.41; H, 4.41; As 16,60; P 6.40; S 13,52.

C20H20AsO2PS2.

Calculated, %: C, 51.95; H, 4.37; As 16.22; P 6.70; S 13.44.

The balance on the device for molecular-film distillation allocate 6.0 g (50%) S-diphenylarsinic-O-methyl-4 - methoxyphenylacetate (3) when the temperature of thermocouple 170-185oC (0.03 mm RT.cent.), n2D01,6818.

An NMR spectrum31P (Bruker CXP-100, 36.5 MHz, C6H6, p, M. D.): 95.4. Range PMR (Varian T-60, 60 MHz, C6D6internal standard (Me3Si)2O , M. D., J, Hz): to 3.02 (s, 3H, CH3O-C6H4) 3.40 (3H D., CH3OP,3Jp-n15,0); 6.40 (doctor d, 2H, 3,5-H2C6H2,3Jn-n9.0,4Jp-n4.0); 6,68-the 7.43 (m, 10H, C6H5); 7.79 (doctor d, 2H, 2,6-H2C6H2, 3Jn-n9.0,3Jp-n14.0). IR-spectrum (Fourier transform infrared spectrometer Bruker IFS 113, the liquid film , cm-1): 3069 O. SL, 3052 O. SL (=C-H, Ar); 2940 O. SL, 2895 CL (CH3as, s), (CH2as, s); 1595, 1501 cf (C=C, Ar); 1258 s, , (CH2); 1026 c /(P)-O-C/ a; 830 Wed, 802 cf /P-O(C)/; 692 (P=S), (PS2as); 532 cf (P-S), (PS2s); 475 cf (As-S); 390 cf (As-S). Mass spectrum (Hitachi M-80-B, PI, 70 eV), m/z (IRel., %): 462 (M)+(23); 385 (M-C6H5)+.(10); 353 (M-C6H5-S)+.(5); 308 (M-2C6H5Rel., %): 108 (M + H - MeOPS - SAs (C6H5)+2(15).

Found, %: C, 52.20; H, 4.20; As 16.68; P 7.65; S 14,40.

C20H20AsO2PS2.

Calculated, %: C, 51.95; H, 4.37; As 16.22; P 6.70; S At 13.84.

Thus, the inventive method provides for the achievement of goals. The peculiarity of this method is the use of fosforireostuse compounds containing the group , which used 2,4-bis(4-methoxyphenyl)-2,4-dicicco - 1,3,25, 45- dithiadiphosphetane. Furthermore, the method allows to achieve good yields of products (71-80%), the method is simple, because it allows one to obtain S-dialkyl-, alkylphenyl and diphenylarsinic esters of 4-methoxyphenylacetone acid in one stage, proceeding directly from industrially available 2,4-bis(4-methoxyphenyl)-2,4-dicicco-1,3,25, 45- dithiadiphosphetane.

The method allows to obtain the target products in pure form, because it precluded the formation of any side products.

The mild reaction conditions allow to save energy in the claimed method.

1. The method of obtaining S-dialkyl-, alkylphenyl or diphenylarsinic esters of 4-methoxyphenylacetone sour the sludge;

R" is lower alkyl, phenyl,

wherein the 2,4-bis(4-methoxyphenyl-2,4-dicicco-1,3, 25, 45-dithiadiphosphetane subjected to interaction with alkylamino or phenyl esters of dialkyl-, alkylphenyl or diphenylarsinic acids of General formula

R0AsR'R",

where R, R', R" have the above values,

at 20oC, followed by separation of the target product.

 

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