SU1643550A1 - 2-diethoxyphosphoryl-6-diphenylphosphorylphenol exhibiting growth-inhibiting activity - Google Patents

Abstract

The invention relates to phosphorus, h 5 4 2 nical substances, in particular 2-diethoxiphosphoryl-6-diphenylphosphorylphenol, which exhibits growth-inhibiting activity, which can be used in agriculture in the fight against lodging of cereals. The goal is to create. new more active substances of the specified class. Synthesis is carried out by the reaction of (2-diethoxyphosphoryl) phenyl ester of diphenylphosphinic acid with lithium diisopropylamide in dry tetrahydrofuran medium at (-60) ° C in a stream of dry argon, followed by raising the temperature to room temperature and stirring for 2 hours. Yield 55%, mp, 79-81%, gross f-la C2 gH2405P2, toxicity mg / kg, stem length of wheat seedlings in% of the control (at a concentration of 0.005%) 60 versus 71 for etrela. 1 tab.

Description

The invention relates to the chemistry of organophosphorus compounds, in particular to a new compound 2 — diethoxyphosphoryl — 6 — diphenylphosphorylphenol of the formula

These applications in agriculture as a plant growth regulator in the fight against lodging of cereal crops.

Compound (ί) is new; its synthesis and properties are not described in the literature.

SLE

SL SP

Known plant growth regulator - etrel, which is used to combat lodging of cereal crops and is selected as an analogue in action and serves as a standard in determining

growth inhibiting active compounds (I).

The indicated compound possesses growth — inhibitory activity, and 2 — diethoxyphosphorp are chosen as structural analogues. (phenol (il) and 2-diphenylphosphorylphenop (ϊ .11):

he (p) (W) ’The aim of the invention is to search for New compounds with growth - inhibitory activity that are superior in. activities known used in agricultural growth regulators;

Connection (i) to the general scheme:

get in the wake of kg

II

Ph ₂ P-Cl pyriEin

HE

1. LiN (iP ₂ ) ₂ / ^p (OEt) ₂

2. HgO (I)

(I) where Et

Ph

- ethyl; phenyl.

Growth inhibitory activity is determined by the deviation from the control of the linear sizes of plant organs grown on media containing the test compound.

Example 1. Synthesis of (2-diethoxyphosphoryl) phenyl ester of diphenylphosphinic acid (IV).

To a solution of 5.0 g (22.0 mmol) of 2-di · ethoxyphosphorylphenol in 50 mp absolute benzene, 1.7 g (22.0 mmol) of dry pyridine are added at the komlso, extracted with benzene (3 / c. Temperature, After ten minutes stirring 5.2 g (22.0 mmol) of diphenylphosphinic acid chloride are added to the reaction mixture, The reaction mixture is boiled 2,

2.5 h, cooled and poured into 10Q mp water. Separate the organic layer, water x <30 mp). Combine benzene extracts, 3), sodium bicarbonate and evaporate in vacuo. The residue was recrystallized from _{mixture ί 5} , si benzene-hexane. 5.7 g of (IV) are obtained, mp 65-67'C.

Found,%: C 61.8, 61.7; H 5.8, 5.5; P 14.2, 14.3, ^C 22 ^H 24 ° S ^P 2.

Calculated,%: C 61.4; H 5.6; P 14.4. l

PMR (acetone-dg): 0, ppm. 1.26 (t, 6H, 31 _ni = 7.5 Hz, -CH ₃ ); 4.16 (m, 4H, -P-CH ^) ·, 7.10-8.32 (Μ, 4H, aroma of protons),

NMR ^{3 <} P (acetone-d,), ppm: 15.73, 30.95,

PRI me R 2, Synthesis of 2-diethoxy-phosphoryl-6-diphenylphosphorylphenol (I).

A solution of 5.3 g (10.0 mmol) (IV) in 25 mp dry tetrahydrofuran (THF) is cooled to -60 ° C and, with stirring in a stream of dry argon, a solution of lithium diisopropylamide obtained from 1.2 g (12.0 mmol) diiso-propylamine and 4.8 ml of 2.4 N solution of butyllithium in hexane. The reaction mixture was stirred for 45 min at -60 ° C ^minutes, then the cooling bath was removed, the temperature was raised to room temperature and stirred for another 2 h, the reaction mixture was evaporated, to the residue was added 15 cpx hydrochloric acid (1: 3). And the mixture was extracted with chloroform (3X15 MP) . The extract was washed with water, dried with sodium sulfate and evaporated in vacuo. The residue is chromatographed on a column with silica, washed with hydrochloric acid (|; water) (3X30 mp), dried with sul gel (eluent; chloroform, chloroform 3.5% ethyl alcohol). 2.4 g of (I), 55%, t are obtained. mp 79-81 ° C (ether-hexane).

Found,%: C 61.0, 60.9; H 5.7, 5.5; P 14.0, 14.2.

^C 22 ^H 24 * 35 ^R g · Calculated,%; C 6i, 4; H 5.6; R . 14.4. .

⁵ PMR (CDClj) O, ppm: 137 (t. 6 H, 3 1 _{я i} = 7.5 Hz, —CH ₅ ); 4.17 (m, 4H, -P-CHg-); 7.00-7.95 (m, 13H, aroma, protons),

NMR ^E, P (CDC1.) Ί, ppm: 19.561

32.55.

Example Z. The growth inhibitory activity of compounds (l) - (ill) was evaluated in a laboratory experiment. Dough object: wheat seedlings ’’ Mironovskaya - 808 ”. The effect of substances on plant growth is assessed by the deviation from control of the linear sizes of plant organs grown on media containing the test substance. As a reference, an etrel retardant is widely used in the practice of combating lodging of crops. For experiments' 45, three-day-old seedlings are selected that do not have defects in the root systems · !, with a coleoptile dayne of 3-3.5 cm. In the future. plants are grown on Knop's medium under a fluorescent lamp under 7-kick lighting with an 18-hour light period at 20-24 ° C. After 12 to 12 days, the length of the stem and the second leaf of the plant is measured. The experiments were repeated three times, in each repeated; 25 to

I * ty not less than 15 plants. The results of the experiments are shown in the table. It’s against the wall that compound (l) is superior to etra in structural growths of bioperformance activity and structural analogs (I) n (Ill) t Oral toxicity is determined on white mice. The value of Led>> 1000 mg / kg. According to the classification, this substance can be classified as slightly toxic.

Claims (2)

The claims of the invention! 2-Diethoxy phosphoryl-6-diphenyl phosphoridphenol of the formula exhibits growth-inhibiting activity. G Substance Concentration, 2 The length of the parts pr < X from to -------4 Fostkov Wheat Stem length Length of the second leaf I 0.01 57 12 0.005 60 31 0.0025 65 42 0.001 92 81 II. 0.01 92 89 III 0.01 98 100 Etrel 0.005 71 56 0.0025 76 60