DE1568138A1 - Process for the production of biscarbamates - Google Patents

Description

BADISGEE ANIIIF- & SODA-FABRIK AG * CGQIOQ

Our sign O ₀ Z, 24 330 Schs / Gn üjudwigshafen am Rhein, 5 »7» 1966

^ ^r experience en_zu r. Manufacture of bis.carbamates

It is known j isocyanates or carbamic acid halides _e implement to urethanes with alcohols. I ^ hydroxyl groups with an acidic character, like those of the phenols, only react with isocyanates at a higher temperature, for example in the reaction of i-naphthol with methyl isocyanate.

It was found that valuable biscarbamates (diurethanes) the Pormel. .. "■■"., ■

in which X is oxygen or sulfur, R ^{r is} an aliphatic radical optionally substituted by chlorine, bromine or methoxy or ■ ethoxy groups with 1 to 8 carbon atoms and R. is an aliphatic radical optionally substituted by chlorine, bromine or methoxy or ethoxy groups 1 to 8 carbon atoms, the naphthyl radical,

the benzyl radical or the rest
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where η the numbers O, 1, 2 or 3, R "chlorine, bromine, iodine, Fluorine or a lower alkyl group, the trifluoromethyl group, a lower alkoxy group, the Methy! sulfonyl-, Mtro-, Dialkylamino, cyano, carboxyl, carbalkoxyl or carbonamide group or a cycloaliphatic radical having 6 to 12 carbon atoms which is optionally substituted by lower alkyl in the ring or a di- or tricyclic cycloaliphatic Radical and R "'means hydrogen or a lower alkyl radical, if one is a hydroxyphenyl carbamate or Hydroxyphenyl thiocarbamate of the formula

KH-CX-OR '

in which X and R 'have the meanings given above, *, with a Isocyanate or carbamic acid halide of the formula

or Ii-CO-Y

in which Y is chlorine or bromine and R and R ¹ ″ have the abovementioned meanings, is reacted in a manner known per se, the reaction with the carbamic acid halide taking place in the presence of an acid-binding agent.,

0.2. 24-330 "

The new compounds tend to crystallize well Products that have good herbicidal properties. They are effective for both selective and total control of plants by mixing the active ingredients with Usual solid or liquid carriers are used to obtain herbicidal agents =

The process of making the new compounds is in progress according to the general reaction equations a or ho.

Η0- /

R-HH-C-O

b R-NH-C-Y + HO-

HH-C-ÖR ¹ X

-HY

E-HH-O-O 0

where X, R, R ¹ and Y have the meanings given above

As starting products for the manufacturing process according to the invention e.g. m-Hydroxyphenylcarbamate come into consideration, the reaction products of chlorocarbonic acid methyl, ethyl, propyl, isopropyl, butyl, isobutyl, isoamyl, allyl, methallyl-, buten- (i) -yl- (3) -, butyn- (i) -yl- (3) -, or thiometfayl-, thioethyl, thiopropyl, thiobutyl, thioisobutyl esters with m-aminophenol. Their manufacture can be carried out in

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Presence of hydrogen chloride binders, e.g. tertiary Amines or alkali carbonates.

As isocyanates, which are used as starting products for the erfinduhgsgemäße Manufacturing processes come into question are ß-chloroethyl, isopropyl, 3-methylcyclohexyl, cyclooctyl, Cyclododecyl-, 2,4 ~ dimethylcyclohexyl-, cyclohexyl-, ο-, m-, p-chlorophenyl-, o-, m-, p-methy! phenyl-, xylidyl-, o, m, p-anisidyl-, m, p-fluorophenyl, ΐη, ρ-bromophenyl, p-iodophenyl, 3,4-dichlorophenyl-, 3-01110 ^ 4 ^^ 11 ^ 116 ^ 1-, or 4-chloro-3-bromophenyl-, 4-chloro-3-methylphenyl-, 3-chloro-4-methylphenyl-, 2-chloro-3-methylphenyl-, m-, p-trifluoromethylphenyl-, 4-chloro ~ or 4-bromo-3-trifluoromethylphenyl ~, 3-nitrophenyl-, 4-chloro-3-nitrophenyl-, m-cyanophenyl-, o-carbomethoxyphenyl-, m-Carboamidophenyl-, m-Carboethoxyphenyl-, p-Methylsulfonyl- ' to name phenyl isocyanate. Furthermore, the iso- ' eyanates corresponding carbamic acid halides are used will.

The reactions according to the invention of the two starting materials took place in solution and, in fact, inert solvents, for example dioxane, tetrahydrofuran, ether, hydrocarbons, chlorobenzene and the like, are used. The reaction is carried out at temperatures of 15 to 150 ⁰ C, preferably between 30 and 8O ⁰ C. There are approximately equivalent

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Amounts of the starting materials used for the reaction "· The reaction with the carbamic acid halide is carried out in • the presence of an acid-binding agent, ZJO a tertiary amine, 'amino alcohols, - alkali metal alcoholate, alkali metal carbonates or alkali metal hydroxide _o

The following examples are intended to explain the reactions according to the invention. - "

example 1

To 16.7 parts by weight (Gwtln.) Nm-Hydroxyphenylcarbamin- säuremethylester dissolved in 50 parts by volume of tetrahydrofuran and a trace of triethylamine are added dropwise with stirring "at 4-0 to 50 ⁰ C 18.7 Gwtle. M-trifluoromethylphenyl isocyanate. It is then fed at The reaction is completed at 60 to 70 ^° C. for 3 hours. Part of the solvent is evaporated off in vacuo and the reaction product is obtained in crystalline form by adding petroleum ether. raethylcarbamat, mp 157-158 ⁰ C:

CP ₅

H-HC-OCH ₅

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Example 2

At 16.7 Gwtln. Nm Hydroxyphenylcarbaminsäuremethylester dissolved in 50 parts by volume of dioxane and a trace of sodium methoxide are ■ · with stirring at 30 to 40 ⁰ O 13.7 Gwtle. p-Fluorophenyl isocyanate was added dropwise, the reaction taking place in part. To complete the reaction, the mixture is ^{heated to 60 to 70 °} C. for a few hours. Part of the solvent is distilled off in vacuo and the 3- (4'-fluorophenylcarbamoyl) oxyphenyl methylcarbamate is obtained in crystalline form by adding petroleum ether. The yield is 29 parts by weight. The substance has a melting point of 161 to 163 ^° C

Example 3

At 16.7%. ΪΓ-m-Hydroxyphenylcarbamic acid methyl ester, dissolved in 50 parts by volume of tetrahydrofuran and a trace of pyridine are ^{stirred at 35 to 45 0} C 14.9 Gwtle. m-anisidyl isocyanate was added dropwise. The reaction mixture is then stirred at 60 to 70 ^{° C. for some time.} After some of the solvent has been removed in vacuo, petroleum ether is added and the product 3- (3'-anisidylcarbamoyl) oxyphenyl methyl carbamate is crystalline in a yield of 30 parts by weight. obtained with the Pp 131 to 133 ° ö.

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TS68138

If, instead of m-Anisidylisocyanat the m-toluyl isocyanate, is obtained in otherwise the same manner as described above, the 3 ~ (3'-Toluylcarbamoyl) ~ oxyphenylmethyl-carbamate; mp 132-133 ⁰ C-

Example. ; 4

If, in the process according to Example 3, 4-chloro-3-trifluoromethylphenyl isocyanate is used instead of m-anisidyl isocyanate, then ^{3-(4 r-} chloro-3'-trifluoromethylphenylcarbamoyl) -oxyphenyl-methylcarbamate with the pp 184 to 186.5 is obtained ⁰ Co

.Y

Example 5

In 20 volumes of tetrahydrofuran there is 10.3 weight percent. m-Hydroxyphenylcarbamic acid isobutin-d) -yl- (3) -ester and a drop of triethylamine dissolved. l) are added dropwise azu starting 8,2 Gwtle- mrToluylisocyanat under stirring at 3O ⁰ C and then the mixture is allowed at 60 to 65 ⁰ C for a time to react. The solvent is evaporated off in vacuo and the residue is recrystallized from methylene chloride. 17 are obtained Gwtle ₀ 3- (3'-Toluylcarbamoyl) -oxyphenylisobutin- (i) -yl (3) -carbamate; Pp 136 to 138 ⁰ C

: -c ~ ocH

O ^ C = CH

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If, with otherwise the same procedure, the m-anisidyl isocyanate is used instead of m-toluyl isocyanate, then 3- (3 ^l »anisidylcarbamoyl) -oxyphenyl-isobutyn- (i) -yl- (3) - ■ carbamate with the pp 135 to 138 ^{0 is obtained} C.

Example 6

At 8.35 weight percent. Nm Hydroxyphenylcarbaminsäuremethylester dissolved in 50 parts by volume of dioxane, 5 Gwtle, pyridine, and with stirring at 25 to 3O ⁰ C 8.5 Gwtle. IT-methyl-N-phenylcarbamic acid chloride, dissolved in 30 parts by volume of dioxane, added dropwise and then heated to reflux for 3 days. After cooling, the chlorine hydrate is separated off by filtration and the solution is concentrated -N ~ phenylcarbamoyl) -oxyphenyl-methylcarbamate with mp 124 to 126 ⁰ C obtained,

Some of the new compounds are listed below and characterized by melting points, where R, X, R ¹ and R ″ mean the various substituents of these compounds:

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X R "R" η

0 3 '-Gl- 5'-CH ₃ 1 -CH ₃ 152 up to 154 ⁰ C 0 3 '-GH ₃ CVJ -CH ₃ 155 up to 157 ⁰ C 0 2 • -C1 "■ .3'-KO ₂ " 1 * -GH ₃ 120 up to 122 ⁰ C 0 X '-Gl 2 -CH ₃ 220 up to 225 ° C 0 CVJ '-JOCH ₃
0 3'-CH ₃ 1 -CH ₃ 189 up to 191 ° C 0 2 • -C1 4'-GH ₃ 2 -CH ₃ 141 , 5 to 143 ⁰ C 0 ' 3 • -01 2 -CH ₃ 171 , From 5 to 172.5 ⁰ C 0 4th '-Cl 4'-Cl 1 -CH ₃ 177 to 178 ⁰ C 0 3 '-Gl - 1 -CH ₃ . 189 up to T91 ° G 0 4th • -J - 1 -CH ₃ 183 up to 184 ⁰ C 0 4th • -F - 1 "C ₄ H ₅ 162 up to 163 ⁰ G 0 4th • -F 1 -C ₃ H ₇ -I 158 up to 160 ⁰ G 0 3 '-GH, 1 -CH ,, -! 136 up to 138 ⁰ C

R R '■ - m.p.

0 , • t-naphthyl -CH ₃ 170 to 171 ⁰ G 0 2-methylcyclohexyl -CH ₃ 166 to 167 ⁰ O 0 2-ethylhexyl -GH ₃ syrup 0 Cyolopctyl -CH ₃ 98 to 100 ⁰ G 0 Benzyl -CH ₃ 132.5 to 134 ^° C 0 Tetrahydrodioyclo-
pentadienyl -CH ₃ syrup

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The following experiments "prove the good effect of the compounds prepared according to the invention.

Attempt 1

The plants Beta vulgaris (beets), Stellaria media (chickweed), Chenopodium album (white Goose foot), Urtica urens (small nettle), Matricaria chamomilla (chamomile), Sinapis arvensis (field mustard), Poa annua (einjo bluegrass) at a height of 2 to 10 cm im Post-emergence and Gossypium sp. (Cotton), Zea mays (Maize) in the undersheet method with 2 kg of 3 ~ (4'-fluorophenylcarbamoyl) -oxyphenyl-methylcarbamate (I) per hectare, dispersed in 500 liters of water treated. After 1 to 2 weeks it was possible it is found that the weeds Stellaria media, Chenopodium album, Urtica urens, Matricaria chamomilla, Sinapis arvensis and Poa annua were almost completely dead, while the beets, cotton and maize continued to grow without damage.

Attempt 2

An agricultural area covered with Stellaria media (chickweed), Chenopodium album (white goose foot), Urtica urens (small nettle), Matricaria chamomilla (chamomile), Sinapis arvensis (field mustard) and Poa annua (bluegrass) was overgrown, the weeds were at a height of

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3 "to 7 em with 3- (4 ^f -Fluorp <henylearbamoyl) -" oxyphenylmethylearbamate (I.) at an application rate of 5 kg of active ingredient per hectare, dispersed in 500 liters of water. that the weeds Stellaria media, Chenopodium album, Urtica urens, Matricaria chamomilla, Sinapis aryensis and Poa annua were almost completely dead. »Then the suffering can be tilled again without harming the plants

Are biologically as effective as I in Yersuch 1 and 2?

3 -C3 ^T -trifluoromethyl-phenyl-carbamoy1) -oxyphenylmethylcarbamate. ■

3- ^ Plienyl-carbarao; y'l) "Oxyphenylmethylcarbamate.

3 ~ (3 'Anisidyl-'carbamoylJ-oxyphenyl-butyne-Ci) -yl- (3) ~ carbamate

3- (3 ' »■ Toluylcarbamoyl)" - oxyphenyl-butyn (1) -yl (3) "carbamate. 3 - (- 2 ^r -Garbomethoxyphenylcarbamoyl) oxyphenyl-methylcarbamate 3- (Tetrahydrodicyclopentadienyl'-oarbamoyl) -oxyphenylme thyIcarbamate

3- (2 ', 3', -β '-Trichlorben ^ yl-carbamoyl) oxyphenyl-methylcarbamate

3 "(3 ', 4'-dichlorophenyl-carbamoyl-I-oxyphenyl-methylcarbamate

In the greenhouse, loamy sand soil was filled into plastic pots with a diameter of 8 cm and the seeds Oryca sativa (rice), Gossypium Bp ₀ (cotton), Zea mays (maize), P.isum

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sativum (peas), Stellaria media (chickweed), Chenopodium album (white goose foot), Urtica urens (small nettle), Matricaria ohamomilla (chamomile), Sinapis arvensis (field mustard), Poa annua (einj "bluegrass), Alopecurus myosuroides (black foxtail), Panicum crus galli (chicken millet) sown. The soil prepared in this way was then coated with 3- (isopropylcarbamoyl) oxyphenylmethylcarbamate (I) and in comparison with N-3,4-Diehlophenyl ~ methylcarbamate (II) in each case an application rate of 3 kg of active ingredient per hectare, dispersed in 500 liters of water treated. After 4 to 5 weeks it was found that I had a stronger herbicidal action than was recorded at II. The herbicidal effect can be seen from the table below;

Active ingredient I. 0 II 0 Hat plants i 10 0 Rice. ■ 0 to 10 0 to 10 cotton 0 Corn 80 10 peas 100 Unwanted plants; 100 60 to 70 Chickweed 90 to 100 70 white goosefoot 70 small nettle 50 chamomile

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The plants Oryca sativa (rice), Gossypium sp. (Cotton), Zea mays (maize) using the uterine leaf method and the plants Pisum sativum (peas), Stellaria media (chickweed), Chenopodlum album (white goose foot), Urtica urens (small nettle), Matricaria chamomilla (chamomile), Sinapis arvensis (field mustard), Poa annua (aj. Bluegrass), Alopecurus myosuroides (black foxtail), Panicum orus galli (chicken millet) in the usual way with a Growth height of 2 to 10 cm with 3- (isopropyloarbamoyl) -oxyphenyl-methyloarbamate (I) and, in forget, with N-3,4-Diohlophenylmethyloarbamat (II) in each case at an application rate of 3 kg of active ingredient per hectare, dispersed in 500 liters of water treated. After 3 to 4 weeks you could see that I had a stronger effect than II. The herbicidal effect is shown in the table below see:

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1568 138 0 Active ingredient II Crops t 10 rice 10 0 cotton until 10 10 bia 20th Corn 90 0 peas 100 10 Unwanted plants 100 Chickweed 90 until 100 60 to 70 white goosefoot 100 70 to 80 small nettle 80 90 chamomile 80 until 100 70 Mustard 80 90 einj "grasses to 90 70 to 80 Black foxtail 60 Chicken millet 50 to 60

0 = without damage
100 = total damage

Biologically as effective as I in experiments 3, 4 and 6 are t

3- (Isoprop.ylcarbamoyl) oxyphenyl isopropyl carbamate 3- (Methylcarbamoyl) -oxyphenyl-isopropyloarbamate 3- (Methylcarbamoyl) -oxyphenyl-butyn- (i) ~ yl ~ C3) -cart> amate

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Versuoh 5

A test surface with Stellaria media (chickweed), Ohenopodium album (common lambsquarters), Urtica urens (small nettle) Matricaria chamomilla (chamomile), Sinapis arvensis (wild mustard), Poa annua (ay ₀ bluegrass), AIopecurus myosuroides (blackgrass) , Panicum crus galli (chicken millet) was sown, was sown on the day of sowing with ^ - (iBoprppylcarbamoylJ-oxyphenyl-methylcarbamate (I) and, in comparison, with 2-chloro »-4,6-bis- (ethylamino) '- s-triazine (II) sprayed at an application rate of 7.5 kg of active ingredient per hectare, dispersed in 500 liters of water.Wake 3 to 4 weeks it was found that active ingredient I had completely killed the weeds and grass weeds, while with the active ingredient II the weeds were not completely dead »

Trial 6

An agricultural Uutzflache, di-e with Stellaria media (chickweed), Ohe'nopodium album (white goose foot), Urtica urens (small nettle), Matricaria chamomilla (chamomile), Sinapis arvensis (mustard), Poa annua (einj ₀ bluegrass), Alopecurus myosuroides (black foxtail), Panicumcrusgalli (chicken millet) was overgrown with 3- (isopropylcarbamoyl) -oxyphenyl-methylcarbaniate (I) and, in comparison, with

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2-chloro-4,6- "bis- (ethylamino) -a-triazine (II) in each case an application rate of 7.5 kg of active ingredient per hectare, dispersed sprayed in 500 liters of water «After 8 days, the weeds and grass weeds treated with active ingredient I showed a · severe damage, while the plants sprayed with II still showed normal growth. After 3 weeks were almost all plants completely dead,

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Claims (1)

Claim Process for making τοη biscarbamates of the formula 33 " X is oxygen or sulfur, R ¹ represents an optionally chlorine- ₉ bromine or methoxy-.or Ithoxygruppen substituted aliphatic radical having 1 to 8 carbon atoms and R a is optionally substituted by chlorine, bromine or methoxy or Ithoxygruppen substituted aliphatic radical having 1 to 8 carbon atoms , the naphthyl radical, the benzyl radical or the rest where η the numbers 0, 1 »2 or 3 and R" chlorine, bromine, iodine, fluorine or a lower alkyl group, the i-drifluoromethyl group, a lower alfcoxy group, di% methylsulfonyl, nitro, _f dialkylamino, cyano, carboxyl, Carbalkoxyl or carbonamide group or a cyoloaliphatic radical optionally substituted by lower alkyl and having 6 to 12 carbon atoms in the ring or a di- or tri-cyclic cycloaliphatic seat and R "'is hydrogen ... "18- ' 909882/1744 - 18 - OoZo 24 330 or denotes a lower alkyl radical, characterized in that a hydroxyphenyl carbamate or hydroxyphenyl thiocarbamate of the formula -CX-OE ¹ ■ in which X and R 'have the abovementioned meanings, with an isocyanate or carbamic acid halide of the formula R-N = C = O or N-CO-Y, in which Y is chlorine or bromine and R and R " ^{1 have} the meanings given above," is reacted in a manner known per se, the reaction with äßm carbamic acid halide taking place in the presence of an acid-binding agent, BADISCHE ANILIN- k SODA-FABRIK AG 0 9 8 8 2/1744