前苏联专利SU1468418A3 Method of producing 2h-chromes

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专利摘要:
The invention relates to substituted heterocyclic substances, in particular cT H jnony4e2 # H 2H ;;; 2cpoMeHoB common ph: CR CR GB CRb-C-C-CH CH-CR, where RJ and RJ are lower alkyl; K is hydrogen, lower alkyl or ketoxy; R is hydrogen; R is ethoxy-, n-propoxy-, isobutoxy-, isopropoxy-, sec-butoxy-, propargyloxy group; Rg is hydrogen or methoxy, which can be used; in agriculture, to combat pests of various crops. The purpose of the invention is the creation of new substances with activity not characteristic of the specified class. Their synthesis is carried out by boiling an appropriately substituted phenol with an acetylene derivative: СНеС — where R, and R — see above; X is a halogen, in the presence of a base and a catalyst — an alkali metal halide (KJ) in a bipolar aprotic solvent. As the latter, it is advisable to use acetone or K, L-dimers formamide. Then, the obtained substance is cyclized with N, N-dimethyl- or N, N-diethylaniline at 190-210 C. New substances will almost completely inhibit the development of insects — cotton mites, cabbage larvae, potato beetles, and houseflies. Animal toxicity LDj; o 200-1200 mg / kg. 1 hp f-ly, 7 tabl .. § From Voa I
公开号:SU1468418A3
申请号:SU843703452
申请日:1984-02-14
公开日:1989-03-23
发明作者:Тимар Тибор；Жупан Кальман；Репаши Янош；Боршош Ирен；Кишш Иштван；Фодор Андраш；Марои Петер
申请人:Алкалоида Ведьесете Дьяр (Инопредприятие)；
IPC主号:

专利说明:

one
The invention relates to a process for the production of new, 2H-chromenes, which are analogous to e of the natural substances Precosen-1 (PI) and Precosen 2 (P2), have biological activity against insects, and can be used as new means of combating pests in agriculture.
The purpose of the invention is to obtain the legs of the 2H-chromenes, possessing valuable, biologically active properties.
The purity of the preparation of the compounds is monitored by thin layer and gas chromatography, and their structure using IR, NMR spectra and mass spectrometry,
Example. 7-n-Propoxy-8-Methoxy-2,2-dimethyl-2H-chromen.
Suspension 5.5 g (30 mmol) of 2-met-hydroxy-3-n-propoxyphenol, 6.5 g
(60 mmol) 3-chloro-3-methylbut-1-yne, 5 g of potassium carbonate and 8 g of potassium iodide in 50. ml of absolute acetone are boiled under stirring for 20 hours. The inorganic salt is sucked off with a-residue after evaporation of the filtrate boil for 8 hours in 100 ml of K, N-dimethylanilinoo. After this, the reaction mixture is left to stand overnight and then decompose with 200 ml of 5% ammonium chloride solution. After conventional work up and purification using column chromatography (silica gel-60; eluent mixture of hexane and ether in the ratio 9: 1), a colorless oily liquid is obtained. The output of 5.8 g (80%).
The resulting intermediate product j (-dimethylpropargyl) hydroxy-2-methoxy-3H-propyloxybenzene (a colorless oil) is reacted with the following NMR and MS data.
H-NMR (CDCl.j) s 1.02 (3N, t, j 7 Hj,); 1.65 (6H, S); 1.8 (3N, m); 2.6 (W, S); 3.8 (3N, S); 3.85 (2H, q, He); 6.7-7.4 (3N, m).
MS (Ei / M) E: 248 (67%); 233 (100%. In a similar manner, the compounds shown in Table 1 are obtained.
Since the compounds of formula (I) possess biological activity towards insects, they can be used as a new pest control agent. The biological activity of precosenes, their mechanism of action and metabolism are described in numerous publications, according to which the action of these active eeDiecTB is expressed in the disruption of the activity of the corpora allata, which produces juvenile hormones in the body of insects. As a result of studies of natural compounds, it was established that their biological activity depends on the 2 chromene ring.
As a result of research, it is established that known 2H-chromenes, such as 6-methoxy-7-ethoxy-2,2-dimethyl-2H-chromen (RE Zr 3623) and 6- methoxy-7-isopropoxy-2,2- dimethyl-2H-chromen (P4), have significantly high activity.
Determination of the inhibitory effect on the development of insect) 1x and nematocidal action.
Potato beetle
Roundworms Caenorhabditis elegans; Meloidogyne marioni.
50% emulsifiable concentrates of the proposed active substances have the following composition;
Active substance, g 500 Arilan SA, g64,2
Lubrol N13, g40.0
Aromasol, mlTo volume
1000.0
For individual insects and worms x i, the tests are carried out as follows.
Cotton ticks.
Acetone solvents of various concentrations are prepared from the tested active 1X substances. 0.2 µl of the solution was applied using a Hamilton syringe to apply 50 larvae on the back, which are in the second stage of development. The active substance is absorbed by the cuticle. Larvae are kept in a Petri dish with cotton seeds and water. After molting, the degree of development of the surviving colon plants as well as the number of hatchlings removed from the deposited eggs 1 x 1 (cabbage larvae, potato beetle) are determined.
Aqueous solutions of different concentrations are prepared from a 50% emulsion concentrate and sprayed on cabbage. After the liquid has dried on the plants (including the control, untreated plants are placed on 20 larvae in the second stage of development and illuminated for a long time (18 hours under illumination, 6 hours in the dark). Eaten plants, if necessary After the end of the test, the number of dead individuals, the degree of development of the larvae, as well as the morphological changes of the pupae and adult insects are determined.
Colaphellus Sophiae. The two-week-old bitter plants are sprayed with a preparation consisting of
five
0.1 g of active quality, 0.5 ml of dimethyl sulfoxide, 10 μl of 50 EC-additives and 10 ml of water. After the liquid has dried on the plants (including control, untreated blossoms), 20 larvae of the Cola phellus Sophiae, which are at the second stage of development, are placed. Every two days, the detached plants are replaced with fresh, treated in the same way, spread. After the end of the test, the number of adult insects hatched from the pupae was determined. Flies.
The larvae of the flies are incubated in glass vessels of 30 X 100 ml with a nutrient medium consisting of 2 ml of milk, 2 ml of water, 2 g of wheat bran and O, g of saturated alcoholic solution. The active substances dissolve 3 milk, ready 0.1% solutions, which corresponds to 0505% of their concentration in a nutrient medium. After the active substance has been added to the nutrient medium, 25 larvae are placed in the vessels (the active substance is not introduced into the control vessel), which are in the first stage of development, and the vessel is closed with a vat valve. After the development of the pupae, the pupae are removed from the vessels and kept in Petri dishes 25 mm in diameter until the flies are hatched. After the end of the test, the number of the flies that are shown will be determined.
Caenorhabditis elegans.
NGM-arabic plates are applied on non-containing bacteria, 0.5 ml of the active substance solution in acetone is applied, and after drying the solution, 25-30 young worms are placed on them. After 24 hours, the number of live and dead worms is determined.
Meloidogyne inarioni.
Eggs of worms from tomato roots are harvested and kept on filter in sterilized water at 25 ° C until in2 is removed. The hatched larvae are kept for 24 hours in a nutrient medium. On bacteria-free NGM agar plates in petri dishes with a nutrient medium, 0.5 ml of the solution of the active substance in acetone is applied, and after removing the solvent, 5 μp of larva suspension prepared from infected larvae located on the second plate are applied to them.
stage swarm developed:. After 72 hours, the kgg number of live to dead individuals was determined. Results of action on cotton g klyp.a, lnchin sh calustnia, Coldpbt; - lus sophiaes ko G: potato and Caenoihabditis elegans: Table: 2
Toxicity tests were carried out on mice (SGBR genus, ve from 20-26 g). Compounds suspension. Fou in Th-geep, Per, OS. Animals are observed at 7 dcan. The value of LD yyg / kg is calculated from Li (5 Uilooxon, The recipient values of the toxicity of the day of the compounds (I) may be between 200-1200. Data on toxicity LD, for R., RJ and Cd of 200, 250 and 310 mg / kg, respectively.
20

权利要求:
Claims (1)
[1]
1. A way to get a 211-chromen total formula
where R and R.J is the lowest a kil; hydrogen, lower cathoxy;
ti ..
Rj - hydrogen, lower -5 alknl hp; /
R is hydrogen; 355 with ETOXI-, n-propoxy-, kobutoxy-, isopropox-, sec, butsxy, prolarg lock-sigroup;
Rg is hydrogen Ш1Н methox group.
D
about t l and that
phenol of general formula
% HivY
Nb
Bjs RE, - and 6 imu specified
meanings
is reacted with an acetylene derivative of the general formula
UR2
x5RI
where R and R have the indicated meanings;
X is a halogen, in the presence of a base and a halide
alkali metal as a catalyst in a bipolar aprotic solvent at boiling point, the compounds obtained are of the general formula
R.
R
where R ,, R ,, R ,, R4, the specified values
subjected to cyclization with S, S dimethyl or K, N-diethylaniline at 190-210 C.
2, the method according to claim, characterized in that acetone or H, M-dimethylformamide is used as a bipolar organic solvent, potassium carbonate is used as a base, and potassium iodide is used as a base and alkali metal.
Matkl And
N v-Propoksn N
72
iSaran METHYN IeoZutoxy N
73
Methyl.N
Neti V
HcrsranВ
HenmH
No N
tv 8 yatvpN
MetyLV
MethylN
H Ztoksn Methyl 50
H n-Propoxy Methyl 69
H Izchpropok- Menm 78 si
R sec. But-Metin 82 hydroxy
H Izovutok- Metyl 80 s
H Etox Metok- 49
si
I and Propok-Metok-80 Sisi
H sec. But-Metok- 59 ox Sy
N Isopropok-Natok-50 Sisi
15 R.
0.94 (); 1.36 (6H; S); 1.7 C2H; t); 3.8 (2H; t;
); 5.34 (1H; d;): 6.1 &(1H;d;); 6.3 (2H; m);
6.76 (W; d;).
1.24 (6H; d; J-6); 1.36 (6H; S); 4.4 (W; m); 5.34 (IH; d;
); 6.16 (IH; d;); 6.3 (2H; m); 6.76 (IH; d;).
0.96, (6H; d;); , 34 (6H; S); 2.0 (IH; ra); 3.6 (2H; d;
J-3); 5.34 (IH; d; J - iO); 6, i6 (18; d; J-ic); 6.3 (2B; m);
6.76 (IH; d;).
1.32 (3H; t;); 1.36 (bN; S); 2.2 (3H; S); 3.9 (2H; q;
J-6); 5.4 (IH; d;); 6.6 (2H; m); 6.36 (IB; d; J-lO).
0.96 (3H; t; J-6); 1.36. (6H; S); 1.7 (2B; m); 2.16 (3H; S);
3.3 (2Hs.t;); 5.38 (IH; d; J-IO); 6.18 (2R; and); 6.36 (W; d;).
1.24 (6H; d;); 1.36 (6H; S); 2.16 (3H; S); 4.4 (tH; m) 5 5.38 (W; d; J ° 10); 6.16 (2H; m); 6.34 (IH; d;). 0.92 (3H; t; J-); , 22 (3H; d; J-i); 1.34 (6H; S); , 6 (2I; w); 2.18 (3H; S); 4.2 (IH; m); 5.4 (IH; d; J-IO); 6.16 (2H; m); 6.36 (IH; d; J-10).
0.96 (6Hi d; J "7); 1.35 (6H; S;, 0); IH; S; 2.18 (3H; S); 3.6 (2H; d;); 5.4 (IH; d;); 6.2 (2H; m); 6.36 (iH; d;).
1.42 (6H; S; + 3H; t;); 2.1 (3H; S); 4.0 (2H; q; 5.47 (IH; d;); 6.27) H; d; 6.35 (IH; d; J-S); 6.75 (W; d; J-8).
1.05 (3H; t; J "8); I, 42 (6H; S); 1.57 (2H; ra); 2, (3H; S); 3.9 (2H; t; J-6); 5.47 (IH; d;); 6.25 (IH; d; J-IO); 6.35 (W; d;); 6.75 (IH, d;).
1.35 (6K; d; J-6); 1.42 (6H; S); 2.1 (3H; S); 4.47 (H; w); . 5 „45 (Н; d;); 6.25 (IH; d;); 6.35 (IH; d; J-S); 6.75 (H; d;). 0.97 (3H; t; J-8); 1.3 (3H; d;); 1.42 (6H; S); 1.68 (2H; m); 2.1 (3KJ S); 4.25 (IH; m); 5.45 (IH; d;); 6.25 (H; d;); 6.35 (IH; d; J-S); 6.72 (H; d;). 1.05 (6H; d;); 1.46 (6H; S); 2.1 (4H; S-nu); 3.7 (2H; d; J); 5.47 (W; d;); 6.27 (IH; d; J-IO); 6.35 (IH; d; J «-8); 6.75 (IH; d; J).
1.38 (3H; c; J 8); 1.42 (6H; S); 3.8 (3H; S); 4.0 (2H; 4)); 5.44 (W; d;); 6.2 (IH; d; J-10); 6.32 (IH; d; J S; 6.56 (IH; d; J "8).
1.02 (3H; t;); , 40 (6H; S); 1.8 (2H; m); 3.8 (3H; S); 3.83 (2H; q;); 5.42 (1h; d;); 6.19 (IH; d;); 6.32 (IH; d,); 6.56 (IH; d;).
0.96 (3H; t;); 1.24 (3H; d;); 1.41 (6H; S); 1.7 (2H; w); 3.76 (3H; S); 4.2 (IH; m); 5.4 (IH; d;); 6.18 (IH; d;); 6.32 (IK; d;); 6.56 (IH; d;). 1.28 (6H; d;); 1.42 {6H; S); 3.76 C3H; S); 4.44 (IH; m);
5.4 (IH; d; J-IO); 6.16 (IH; d; J-10); 6.32 (1I; d; J-8); 6.56 ().
Pramechane; The NMR spectra are characterized by the following way: chemical shift (number of protogens; ithliplicity; coupling constant, Hz).
Table 2
6-Methoxy-7-sec. butoxy-2,2-dimethyl-2H-chromen
6,7-Diphenipoxy-2,2-dimethyl-2H-chromen
6-Methoxy-7-isobutyloxy-2,2-dimethyl-2H-chromen
Control When treated with acetone, 90-95% of casex 1x remains alive.
Continued table.
Oj
m
t a b l and c a 3
1468418
Processing 50 EC compositions, not
containing the active substance. The content of the active substances P1 and 1 in 50 EC is the x ratio of 0.01, and in the remaining 0.1%,
200 400 200 400 200
400 200
400
44
98
100
100
70
90 20
thirty
12
T ablitsa4
Table 5
Table
Table 7
Reduced None
| T
Separate
individuals
Missing
Separate individuals
Missing
13
s
200 400 200 400 200 400
AO
100
60
73
25
85
ABOUT
ABOUT
468418 4
Table 7
Reduced Missing Reduced
eleven
II
Normal

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法律状态:

优先权:

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