CS199313B1 - Esters of thiophosphoric acid and process for preparing thereof - Google Patents

Description

The subject of the invention is the novel 2- (5-alkoxy, alkylthio, chloro-1-alkyl, cyclohexyl, phenyl-6-oxo-1H-pyridazin-4-oxy) 1,2,3-dioxaphospholan (phosphinanane) -2-thiones and method of their preparation. The novel compounds have ovioid effects.

Related pyridazin-4-yl esters of organophosphoric acids of the formula are known in the literature

R ^c

- R in which R? R ² is alkyl, alkoxy, Ν, Ν-dialkylamido, R ² is alkoxy, alkylthio, N-alkylamido, Ν, Ν-dialkylamido, R 6 is halogen, alkoxy, alkylthio, t is alkyl, cycloalkyl, phenyl and benzyl, X is oxygen , sulfur (art. no. 133 599 and 141 95D ·

New compounds of the formula I have now been found

199 313

199 313 ir

wherein R 1 is -CH 2 -CH 2 -, -CH 2 -CH 2 -CH 3 -CH 3 -, -CH 2 -CH 2 -CH (CH 2) -, -CH 2 -C (CH 2) -, g -CH 3 -, R ² is hydrogen, chloro, alkoxy, alkylthio, in each case having 1 to 3 C atoms in the alkyl groups, R 1 is alkyl having 1 to 3 C atoms, cyclohexyl, phenyl.

At the same time, a process for the preparation of the compounds of the formula I by reaction of 2-chloro-1,3,2-dioxaphospholane-2-thion, respectively, was determined. 2-chloro-1,3,2-dioxaphosphorinan-2-thione of formula II

R ¹

P

Cl (II) in which R1 has the above-mentioned advantage with an alkali salt of 1,5-disubstituted-6-oxo-1H-pyrrole;

dazin-4-ol of formula III (+) (-) M 1 ⁾ 0 In which R and R ^J have already been mentioned M is potassium or sodium in the environment

an organic solvent such as acetonitrile, dioxane, dimethylformamide, dimethylsulfoxide, methyl ethyl ketone, stylish acetate, butyl acetate, tetrahydrofuran at a temperature of 40 to 100 ° C.

The following examples illustrate, but do not limit, the novel compounds of the invention and methods of preparation.

Example 1

2- (5-Methoxy-1-methyl-6-oxo-1H-pyridazine-4-oxy) -1,3,2-dioxioxaphosopholane-2-thion KO, O55 mole of 5-methoxy-1-methyl potassium salt 6-oxo-1H-pyridazin-4-ol in 100 mL of acetonitrile was added 0.05 mol of 2-chloro-1,3,2-dioxaphospholane-2-thione. The reaction mixture was stirred at reflux for 2 hours. After completion and cooling, it was poured into 500 ml of water with stirring. The precipitated solid was collected by filtration and purified by crystallization from toluene. Yield: 11.3 g of white crystalline solid, mp 66-67 ° C, corresponding to 85% yield calculated composition: Calculated for N? CGH HP _lljl3 Calc .: _{11.52% P%} N% S 10.07 (MW: 278.2) Found: 11.28% P 11.81% S 10.06% N

The structure of the prepared substance was proved by ifi and UV spectra.

188 313 ΐδ measured in CHCl-j.

^ (0 = 0) : 1647 cm ¹ V (C-C): 927 -1 om V (C = N) : 1617 om ¹ V (OP): 882 cm ¹ In (C-N) : 1381 om ¹ OP (OP): 835 om ¹

H (C-0): 1032 cm ^{@ -1}

UV measured in CH 2 OH 3

Max max: 213 nm, 284 nm. .

Substances were prepared in a similar manner.

Example 2

2- (1-phenyl-5-methoxy-6-oxo-1H-pyridazine-4-oxy) -1,3,2-doxaphoslan-2-thione mp = 168-170 ° C (yield: 59.1%)

Analysis: calculated: 9.10% P

9.20% P found:

0.42% S 9.81% S

8.25% N 8.10% N .: CHCl L6 in the Y (C = 0) 1650 OM ^1, V (C = N) 1628 cm ¹

UV in CH-jOH:

max: 213 nm, 288 nm

Example 3

2- (5-methoxy-1-methyl-6-oxo-1H-pyridazine-4-oxy) -4,5-dimethyl-1,3,2-dioxaphospholan-2-one ion ²⁰ = 1.5421 (yield) : 68.3)

D

Analysis: calculated: 10.11% P 10.77% S 9.14 <N found: 10.23% P 10.69% S 9.44% N

Ιδ in CHCl ₃ : S ¹ (0 = 0) i 1645 µm ¹ , V (C = N): 1 620 cm ¹

UV in CH ₃ 0H:

max: 213 nm, 286 nm

Example 4 ‘

2- (1-Phenyl-5-methoxy-6-oxo-1H-pyridazin-4-oxy) -4,5-dimethyl-1,3,2-dioxafoafolan-2-one

mp = 91 -  92 ° C (yield; 71.2%) analysis: calculated: 8.41% P 8.70% N 7.61 % N found: 8.60% P 8.71% 3 8.01 % N Ιδ in CHC1 ₃ : C (C = 0) : 1657 cm ¹ , ' V (C = N) : 1628 om ¹ UV in CH ₃ OH ^with max : 214 nm, 296 nm

Example 5

2- / l-phenyl-5-chloro-6-oxo-pyridazin-4-yloxy / -4,5-dimethyl-3,2-dioxaphospholane-2-thione

mp M.p. = 110-111 ° C (yield: 69.1%) Analysis: calculated: found: 8.31% P 8.60% S 8.41% P 8.80% S N, 7.52 N, 7.68

199 313 li in CHCl ₃ : y (0 = 0): 1670 cm ¹ , Ϋ (C = N) with 1612 cm ¹ in CC ¹ ₄ : V (C = 0): 1684 cm ¹ , V (C = N) j 1613 cm ¹

UV in CH ₃ OH:% _aax : 212 in m, 302 nm

Example 6

2- / 5-methoxy-l-methyl-6-oxo-pyridazin-4-yloxy / 6-methyl-l, 3,2-dioxaphosphorinane-2-thione

ⁿ D = 1.5511 (yield: 89.6%) Analysis: calculated: 10.11% P 10.47 % WITH N, 9.14 found: 9.90% P 10.32 % WITH 9, N2% in CHC1 ₃ : V (0 = 0) : 1639 om \ y (C = N) : 1608 cm ' UV c CH, 0H _mDV . 3 'max : 213 nm, 285 nm

Example 7

2- (5-chloro-1-methyl-6-oxo-1H-pyridazine-4-oxy) -6-methyl-1,3,2-dioxaphosphorinan-2-thion m.p. = 78-80 ° C (yield: 84.7%)

Analysis: calculated: 9.97% P 10.32% S 9.02% N found: 10.06% P 10.21% S 9.20% N

H (C = N): 1599 cm -1

213 nm, 296 nm

10.06% P iC in CHCl ₃ : V / 0 = 0 /: 1644 cm ¹ ,

UV in CH ₃ 0H:

max

Example 8

2- (1-phenyl-5-methoxy-6-oxo-1H-pyridazine-4-oxy) -6-methyl-1,3,2-dioxaphosphorinan-2-thione m.p. = 74-76 ° C (yield: 88.0%)

Analysis: calculated: 8.41% P 8.70% N N, 7.61 found: 1 8.43% P 8.71% N 7.60% N iC in CHCl ₃ : γ (C = 0): 1649 cm * - ¹ . in (C = N): 1620 cm ^{@ -1} OT v OHjOHt% : 212 nm, 297 nm

Example 9

2- (1-phenyl-5-chloro-6-oxo-1H-pyridazine-4-oxy) -6-methyl-1,3,2-dioxaphosphorinan-2-thione m.p. = 136-138 ° C (yield: 60.2%)

Analysis: calculated: 8.31% P 8.60% S 7.52% N found: 8.65% P 8.81% S 7.68% N

Ifl in CHCl ₃ : V (0 = 0): 1761 cm ¹ , V (C = N): 1613 cm ¹ in CC ¹ ₄ : (0 = 0): 1685 cm ¹ , V (c = N): 1612 cm ¹

UV in CH ₃ 0H:%

212 nm, 309 nm max

189 313

Example 10

2- (1-diethyl-6-oxo-1H-pyridazine-4-oxy) -5,5-dimethyl-1,3,2-dioxaphthaforinan-6-one m.p. = 114 - 115 ° C (yield: 84.6%)

Analysis: calculated:

found:

IR in CHC1 _3: W (0 = 0):

UV in CH, OH:

max

10.67% P 10.55% P 1646 om

% N, 11.04%

11.33% N 9.51% N

Ϋ (C = N): 1598 cm ^{@ -1}

211 nm, 292 nm

Example 11

2- (5-methoxy-1-methyl-6-oxo-1H-paridazine-4-oxy) -5,5-dimethyl-1,3,2-dioxaphosphorinan-2-thione

mp Mp = 98-99 ° C (yield: 72, 6%) analysis; calculated: 9.67% P 10.01 % WITH N, 8.74 found: 9.65% P 10.19 % with 8.93% N IR in CHC1 _3: V (C = 0): 1645 cm ¹ , in (C = N): ί 1618 cm ¹ UV in CH ₃ OH: λ max ^{: 212 nm} > 285 nm

Example 12

2- (5-chloro-1-methyl-6-oxo-1H-pyridazin-4-oxy) -5,5-dimethyl-1,3,2-dioxaphosphorinan-2-thione m.p. = 160-162 ° C (yield: 83.0%)

Analysis: Calculated: 9.54% P Found: 9.52% P

IR in CHCl * in CC1.

V (C = 0) Ϋ (C = 1652 cm ” ¹ )

0): 1678 cm ¹ ,

98.87% S 10.02% S C (C = N) V (C = N)

N, 8.63

N, 8.86

1602 cm 1602 cm '

Example 13

2- (5-ethoxy-1-methyl-6-oxo-1H-pyridazine-4-oxy) -5,5-dimethyl-1,3,2-dioxaphoreforinan-2-thion m.p. = 95-96 ° C (yield: 84.2%)

Analysis: calculated: 9.26% P 9.58% S found: 9.16% P 9.65% S

IR in CHC1 _3: Y (C = 0): 1645 cm ^1, v (C = N) in the UV-CH ₃ OH: A nax 215 nm, 286 nm

N 8.38% N 8.64%

1615 cm ¹

Example 14

2- (5-ethylthio-1-methyl-6-oxo-1H-pyridazine-4-oxy) -5,5-dimethyl-1,3,2-dioxaphosphorinan-2-thione m.p. = 109 - UO ° C (yield: 76.8%)

Analysis: Calculated: 8.84% P 18.30% S 7.99% N

18.53% N 7.93% N

H (C = N): 1580 cm: 212 nm, 322 nm found:

IR in CHCl3: y (C = 0)

8.76% P: 1636 cm ¹ ,

UV in ₃ ohm max

189 313 Example 15 ’

2- (5-propylthiomethyl-6-oxo-1H-pyridazine-4-oxy) -5,5-dimethyl-1,3,2-dioxaphoafraninan-2-thion m.p. «116 - 117 ° C (yield: 90.1%)

N 7.90% 8.06% N

Analysis: calculated: 8.50% P 18,09% the garbage: 8 _y 51% P 17,76% V CHCl ₃ : V (C = 0) : 1636 cm ¹ Ý (C = N): in CC1 ₄ : V (C = 0) : 1645 cm ¹ , Ϋ (C = N): UV v CH ₃ OH: A max : 212 nm, 321 nm

Example 16

2- / l-ethyl-5-chloro-6-oxo-pyridazin-4-oxy / 5,5 'dimethyl-3,2-dioxaphosphorinane-2-thione

mp = 130 - 131 ° C (yield: 86.3%) analysis: calculated: 9.14% P 9.47% the garbage: 8.98% P 9,61% V I want ₃ : 0 (0 = 0) 1652 cm ¹ V (C = N) in ^CC1 4 : C (C = 0) : 1667 om ' ¹ , V (C. = N) UV v CH ₃ OH ⁵ max : 213 wt, 296 nm

8.27% N 8.47% N cm

Example 17

2- / l-cyclohexyl-5-methoxy-6-oxo-pyridazin-4-yloxy / -5,5-dimethyl «l, 3,2-dioxaphosphorinane-2-thione

mp = 110-112 ° C (yield: 69.8%)

Analysis: Calculated: 7.97% 7 8.25% S 7.21% N Sealed: 7.88% P 8.34% S 7.31% N

IC in CHCI, Ϋ (C = 0): 1639 cm ¹ , ý (C = N): 1620 cm ^-1

UV in CH-jOH:

max

215 nm, 287 nm

Example 18

2- / l-phenyl-5-methoxy-6-oxo-pyridazin-4-oxy / 5,5-dimethyl-3,2-dioxafoBforinan-2-thione

mp = 150-151 C

IR in CHC1 _3: CH-UV in Joh:

glazed (yield: 90.2%)

8.10% P 8.39% N 7.33% N 8.24% P 8.59% N N, 7.24 (i): 1653 cm ^-1 , V (C = N) : 1625 cm ¹

: 216 nm, 296 nm max

199 313

OBJECT OF THE INVENTION

Claims (2)

OBJECT OF THE INVENTION 1, tiofosforeSnej acid esters of the formula I, wherein R ¹ is -CH ₂ -CH ₂ -, -CH (CH) CH ₃ / CH ₃₎ -, -CH ₂ CH ₂ CH / CH ₃₎ -, _-CH2 C / _CH3 / _{CH2 2} ', R ² is hydrogen, chloro, alkoxy, alkylthio each having 1 to 3 carbon atoms in the alkyl groups, R is alkyl of 1 to 3 carbon atoms, cyclohexyl, phenyl. 2. A process for the preparation of compounds of formula I, characterized in that a reagent of the compound of formula II (II) is left to react. Cl wherein R is as defined above, with an alkali SALT-1,5-disubatituovaného-6-oxo-pyridazin-4-ol of formula III (III) wherein R and R @ ^J are as defined above, M is potassium, or sodium, in an organic solvent at a temperature of 40 to 100 ° C.