CS195278B2 - Method of preparing cycloalkano/b/thienyl ureas - Google Patents

Abstract

The invention relates to a process for the preparation of cycloalkano (b) thienyl ureas

Description

The invention relates to a process for the preparation of cycloalkano (b) thienylureas of the formula I or II

wherein X is oxygen or sulfur, Z is hydrogen or (C1-C4) alkyl, Y is hydrogen, (C1-C4) alkyl, halogen, cyano, nitro, acetyl, acetylamino or a radical of the formula R 1 -

NHCONH-, R 1 represents hydrogen or C 1 -C 4 alkyl, R 5; and R 3 denotes as indicated below in Table I: T and b at 1 k and I

R2

R 3 hydrogen alkyl C 1 -C 12 cycloalkyl C 3 -C 6 allyl methallyl

2-butenyl hydrogen alkyl C 1 -C 4 cycloalkyl C 3 -C 6 allyl

2-propynyl

2-propynyl hydroxy alkoxy C1-C6 allyloxy methallyloxy

2-butenyloxy methoxymethyl phenoxy — CH2 —CH2 —OH —CH2 —CH2 —O — CH3 —CH2 —CH2 —S — CH3 —CH2 — CH (ORi) 2 —CH2 — CF3 —CH2 — CN

198278

R2 R3

R2

R3 —CH2 — CO2R1 — NH — CO2R1

O

-II — C — R10

—C — CCI3

Q-04- '

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when n == 0

Table 11 when η - 1 when n = 2 hydrogen

4-chloro

3,4-methylenedioxy 2 (3 or 4) methoxy 4-ethoxy 4-butoxy 4-methylthio

2,4-dimethyl

2,4- dimethoxy

2,4-dichloro-4-nitro

2-methyl-4-bromo hydrogen

4-chloro-4-methoxy and 3,4-methylenedioxy hydrogen or wherein R a and R 3 together with the nitrogen atom to which they are attached denote morpholino, piperidine, pyrrolidine, 4-phenylpiperazine, 4-carbethoxypiperazine, 4 (4-methoxy -phenyl) piperazine, 1,2,3,4-tetrahydroquinoline or a radical of formula

as well as the cis and trans-isomers of these compounds, characterized in that they are a mole equivalent of a compound of formula I or IIa

wherein R 1, R 2, R 3, X, Y and Z are as defined above and U is -CH 2 or CHOH, oxidizes 2 to 8 mol equivalents of an oxidizing agent selected from the group consisting of cerium ammonium nitrate, silver nitrate, chromium oxide and sodium dichromate the presence of an aqueous solution of a solvent selected from acetic acid, acetonitrile, tetrahydrofuran, dioxane, dimethoxyethane and diethylene glycol dimethyl ether, which solutions may comprise nitric acid, phosphoric acid, perchloric acid, or chromic oxide in acetic anhydride at a temperature of 0 to 100 ° C.

In the preferred compounds of the invention of formula I above, and especially in compounds of formula II above, Y, Z and R 1 are hydrogen, wherein X is oxygen or sulfur and R 2 and R 3 are independently of each other as shown in Table III:

Table III

R2 is hydrogen or hydrogen;

C 1 -C 6 alkyl C 1 -C 4 alkyl allyl

C 1 -C 4 alkoxy

2-propynyl methoxymethyl or hydroxy

Particularly preferred compounds of formula I are those wherein Y, Z and R 1 are hydrogen, X is oxygen or sulfur, and R 2 and R 3 independently of one another are hydrogen or alkyl of 1 to 8 carbon atoms.

The process according to the invention is preferably carried out using from 4 to 5 mol equivalents of the oxidizing agent of this kind, and preferably at a temperature of 20 to 60 ° C.

The compounds of the invention are useful as growth stimulating agents for animals such as poultry, fur animals and agricultural animals, and the use of said compounds for this purpose has the advantage of improving feed conversion for said animals. The term "feed conversion" refers to the ratio of feed unit weight per unit of increment, and the improvement in feed conversion means the increase in weight of the feed unit of a given feed.

In practice, the cycloalkanoylbthienyl urea of formula I or II is administered to the animals, usually with or in the feed. However, said compounds may be administered as a subcutaneous implant under the skin of said animal or as a parenteral injection. When administered in the feed to poultry, turkeys, sheep, cattle, goats and the like, the effective amount is usually 0.0001 to 0.8% by weight, preferably 0.001 to 0.04% by weight. urea of formula I or II to increase and improve feed conversion.

When administered to said animals, the active compounds as parenteral injections or subcutaneous implants are administered in an amount of about 0.001 to 0.2 mg, preferably 0.005 to 0.10 mg per kg body weight per day, and the desired gain in weight gain and increase is achieved. feed conversion.

Tests with one day old chickens revealed 1 to 9 ppm

4,5,6,7-tetrahydrobenzo (b) thien-4-ylurea fed to chickens causes a 3.3 to 6.6% improvement in weight gain and also provides a 2.7 to 4.7% improvement in feed conversion.

The compounds of the invention are also useful as herbicidal compositions. They are effective for controlling undesirable broadleaf and grass weeds when applied to soil containing said undesired weed seeds or when applied to foliage of such plants. Usually, 5.60 to 16.8 kg / ha, preferably 9 to 11.2 kg / ha are suitable for such control of undesirable plants.

In the following, the invention is illustrated in more detail by means of exemplary embodiments.

He did

Preparation of 4,5,6,7-tetrahydro-7-oxobenzo (bthien-4-ylurea)

A sample of 6 g of 4,5,6,7-tetrahydrobenzo (bthien-4-ylurea) was dissolved in 375 ml of 50% aqueous acetic acid and 75 g of cerium ammonium nitrate was added in portions over 10 minutes with stirring at 25-35 ° C. The pale orange solution was stirred for an additional 5 minutes, water (100 mL) was added and the solution was extracted twice with ethyl acetate (450 mL).

350 ml) and the combined extracts are washed with 100 ml of water. The organic extract was evaporated to dryness in vacuo and the brown residue was crystallized from methanol; 2.37 g are obtained

4.5.6.7-tetrahydro-7-oxobenzo (b) thien-4-ylurea, m.p. 237-238 ° C. Recrystallization from methanol gave the purified product, m.p. 245-246 ° C.

Similarly prepared is 1-methyl-3- [4,5,6,7-tetr ahydro-7-oxobenzo (bthien-4-yl) urea, 1-ethyl-3- [4,5,6,7-tetrahydro -7-oxobenzo (bthien-4-yl) urea, 1n-hexyl-3- [3,4,5,6,7-tetrahydro-7-oxobenzo (b) thien-4-yl] urea, 1n-dodecyl- 3- [4,5,6,7-tetrahydro-7-oxobenzo (b) thien-4-yl] urea and 1-phenyl-3-l [4,5,6,7,7-tetr ahydro-7-oxobenzo (b) thien-4-yl] urea,

4.5.6.7-tetrahydro-4-oxobenzo (b) thien-7-ylurea, 1-methyl-3- [4,5,6,7-tetrahydro-4-oxobenzo (b) thien-4-yl] urea and optically active isomers of 4,5,6,7-tetrahydro-7-oxobenzo (b) thien-4-yl ureas as described above starting from the corresponding ureas.

Substitution of cerium ammonium nitrate with silver oxide, chromium oxide or sodium dichromate also leads to the above 7-oxo compounds. Chromium trioxide followed by hydrolysis also provides 7-oxo compounds. The above 7-oxo derivatives are also prepared by oxidation of their corresponding 7-hydroxycycloalkano (bthien-4-ylurea) in the same manner.

Preparation of 5,6,7,8-tetrahydro-4H-8-oxocyclohepta (b) thien-4-ylurea

A sample of 5,6,7,8-tetrahydro-4H-cyclohepta (b) thlen-4-ylurea was oxidized with ceric ammonium nitrate as described in Example 48 to give 5,6,7,8-tetrahydro-4H -8-oxocyclohepta (b) thien-4-ylurea, m.p. 246-248 ° C.

Example 3

Mouse growth control assays.

and

CFI female Carworth farm mice six weeks old were adopted. They were put in a cage in a tempered room (22.2 to 24.4 ° C) (72 to 76 ° F) with automatic light control, 14 hours on, 10 hours off. The basal diet used in these studies is “Purina Laboratory Choro” (see description below), which is administered ad libitum. Water is also allowed at will.

Thirteen days after the start, mice were weighed in groups ¹ of 10 and were randomly assigned to different treatments. The concentration of the different compounds in the diet is shown in the following tables. Twelve days later, the mice were weighed again and the experiment discontinued. At least three cages (30 mice) of untreated control mice were included in each experiment. Data are shown in Table IV as percent weight gain versus control. The following is a description of the diet to which the growth enhancing compounds are added.

The feed to which growth-promoting compounds have been added is described below.

Feed

Analysis of crude protein, not less than 23.0% crude fat, not less than 4.5% raw fiber, not less than 6.0% ash, not less than 9.0%

Folders:

meat meal, bone meal, skimmed milk powder, wheat meal, fish meal, animal liver meal, dried lean beet pulp, ground pressed corn, oatmeal, soybean meal, raw sugar molasses, with butylhydroxyanisoleiii preserved animal fat, vitamin Bia pantothen, calcium, choline chloride, folic acid, addition of riboflavin, dried malt, thiamine, niacin, addition of vitamin A, D-activated plant sterol, addition of vitamin E, calcium carbonate, calcium phosphate, iodized salt, ferric ammonium citrate, iron oxide, magnesium oxide , cobalt carbonate, copper and zinc oxide.

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Example 4

The following tests were carried out to evaluate the ability of 4,5,6,7-tetrahydrobenzo (b) thlen-4-ylurea to promote! growth of chickens.

In these experiments, one day old chickens are placed in heated cages and fed and water is given to them at will. There are 5 males and 5 females per cage in each experiment and three cages are used for treatment. Treatment consists of a basal diet plus 1.3 or 9 ppm of the test compound. The chicks weigh at the beginning and end of the experiment. Food consumption is determined for an experimental period that is 13 days from the start when the chicks are one day old. The basal diet used and the results are shown below.

Basic chicken feed

% ground yellow grain 53.45 soya meal (49%) 28.0 menhanden fish flour (60%) 5.0 cereal gluten meal (60 ° / o) 5.0 dehydrated alfalfa flour (17%) 2,0 stabilized fat 4.0 Middle calcium orthophosphate 1,2 ground limestone 0.5 sodium chloride 0.3 ⁺ tra-min # 3 0.05 ^{+ +} vitamin prems 0.5

100.00 ^{+ +} Vitamin mixture per ton

grams DL methionine 453.6 BHT 113.6 Vitamin A (30,000 j / g) 100.0 Vitamin D3 (200,000 J / g) 5.0 Vitamin E (44,093 j / kg) 45.4 riboflavin 4.0 niacinamide 250 Ca pantothenate 8 0 Vitamin K (menadione) 1.0 parvo (10%); 3 0 Choline chloride (50 0/0) 908.0 Proferm (44mg / kg), B12 22 ςθ corn oil 50.0 fine ground corn 2 582.4 4,536.0 ⁺ tra-min # 3 % 0.454 kg / t PPm manganese 12.50 62.5 iron 6.00 30.0 zinc 5.00 25.0 copper 0.65 3.25 iodine 0.35 . 1.75 cobalt 0.25 1,25 calcium 15.30 min.

18.35 max.

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Example 1 a d 5

Evaluation of improved growth and feed in sheep given an implant containing the test compound

To determine the effect of 4,5,6,7-tetrahydrobenzo (b) -thien-4-ylurea on sheep, lambs are randomly selected in groups of six. Sheep are weighed and feed and water allowed at will. Feeding is weighed daily and unused feed from the previous day is collected and weighed. Experimental animals receive. same feed as control animals, but test animals receive one or more subcutaneous implants containing test compound at the bottom of the ear. The composition of the implant used is shown below. At the end of the six-day period the lambs are weighed again and the total feed consumed is counted.

In these experiments, six replicates were used for six lambs per treatment and each animal received from about 11 to 105 mg of the test compound.

The average of the six-week increment is given in Table VI and the in kg / kg feed is shown in Table VII. From these data it is seen that the lambs implantation 11 mg or 99 mg of test compound showing approximately 10 ^iO / o by weight. addition to untreated controls six weeks after implantation. Feed utilization was also improved at the same time by about 5% over untreated controls.

Lamb feed% ground corn cob, 15.0 ground yellow corn 48.0 soybean meal (49%) 10.0 ground dried alfalfa 15.0 molasses 10.0 iodine salt 0.5 medium calcium orthophosphate '1.0 premix' 0.5

100.0

Premix per ton of grams of tramin No. 3 ⁽¹⁾ 454 vitamin A (30 000 j / g) 133 vitamin D3 (200 000 j / g) 5 corn oil 100 milled cereals 3,848

540

Ψ tra-min No. 3% calcium 21.00 manganese '12.50 iron 6.00 zinc 5.00 copper 0.65 iodine 0.35 cobalt 0.25

Implant - pellet mg

4,5,6,7-tetrahydrobenzo (b) thien-4-ylurea. 11.0 glyceryl-12-hydroxystearate 10.50 magnesium stearate 0.50

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OBJECT OF THE INVENTION

Claims (3)

OBJECT OF THE INVENTION A process for the preparation of cycloalkano (b) thienylureas of the formula I or II R2 R3 o tench IL is C1-C4-X where X is oxygen or sulfur, Z is hydrogen or C1-C4 alkyl, Y is hydrogen, C1-C4 alkyl, halogen, cyanogen, nitro, acetyl, acetylamino or a radical of formula R 1 is NHCONH-, R 1 is hydrogen or C 1 -C 4 alkyl, R 2 and R 1 are as shown in Table I below: .ch ₂ Rz Table I R 1 is hydrogen, C 1 -C 12 alkyl, C 3 -C 6 cycloalkyl, allyl. . methallyl, 2. Process according to claim 1, characterized in that from 4 to 5 mol equivalents of oxidizing agent are used at a temperature of 20 to 60 ° C. 2-methyl-4-bromo hydrogen, 4-chloro, 4-methoxy and 3,4-methylenedioxy, hydrogen, or wherein the substituents Ra and R3 together with the nitrogen atom to which they are attached denote morpholino, piperidine, pyrrolidine, 4-phenylpiperazine, 4-carbethoxypiperazine, 4- (4-methoxyphenyl) piperazine, 1,2,3,4, -tetrahydroquinoline or a radical of formula 1 as cis and trans isomers thereof, characterized in that it is a mole equivalent of a compound of formula I or II and (ta) wherein R 1, R 2, R 1, X, Y and Z is as defined above and U is -CH 2 or CHOH, oxidizes 2 to 8 mol equivalents of an oxidizing agent selected from the group consisting of ceric ammonium nitrate, silver nitrate, chromium trioxide and sodium dichromate in the presence of an aqueous solvent selected from acetic acid, acetonitrile, tetrahydrofuran, dioxane, dimethoxyethane and diethylene glycol dimethyl ether, these solutions may contain nitric acid, phosphoric acid, chlorine pure or chromium trioxide in acetethanedfide at 0 to 100 ° C. 2,4- dichloro, _x; 4-nitro a 2,4- dimethoxy, 2.4- dimethyl, 2- (3 or 4) -methoxy, 4-ethoxy, 4-butoxy, 4-methylthio, 2-propynyl, -C-CCl 3, wherein R 1 is as defined above, n is 0, 1, or 2 and Q is selected from the group shown in Table II: 188270 ,. Table II, when η - Ο when η = 1 when η = 2 hydrogen, 4-chloro, 3.4- methylenedioxy, 2-butenylcxy, methoxymethyl, phenoxy, -CH2-CH2-OH, -CH2-CH2-O-CH3, -CH2-CH2-S-GH3, -CH2-CH2OR1H -CH2-CF3, -CH2-CN, -CH2- CO2R1, —NH-GO2R1, II — C-Ri, O hydrogen, C 1 -C 6 alkyl, C 3 -C 6 cycloalkyl, allyl, 2-propynyl, hydroxy, C 1 -C 6 alkoxy, allyloxy, methallyloxy, 2-Butenyl, 3. The process of item 1 for preparing a compound of formula Γ. wherein X is oxygen or sulfur and R 2 and R 1 are each independently selected from the group consisting of: hydrogen and (C 1 -C 8) -alkyl, characterized by the reaction of a compound of formula (Ia ') wherein X, R 2 and R 3 are as defined above, with 2 to 8 mol equivalents of an oxidizing agent selected from ceric ammonium nitrate, chromium trioxide and sodium dichromate in the presence of an aqueous solution of a solvent selected from acetic acid, acetonitrile, tetrahydrofuran, dioxane, dimethoxyethane and dlethylene glycol dimethyl ether, said solutions may comprise nitric acid, perchloric acid or chromic oxide in acetic anhydride at 0 to 100 ° C. Severografiá, n. P., Plant 7, Most