DE1910490A1 - Diarylureas and their use as herbicides - Google Patents

Description

LAWYERS

DR. JUR. DIPL-CHEM-WALTER BEIL ALFREDHOEPPENER

DR. JUR. DlPL-CHEM. H.-J. WOLFP

DR. JUR. HANS CHR. AX

623 FRANKFURT AM ΜΑΪΝ- HÖCHST

ADElONSIRASSt 58

Our No. 15 384

Chevron Research Company, San Francisco * Cal.jV. St. A.

Diarylureas and their use as

Herbicides

The invention relates to a new group of aromatic ureas, in particular N-aryl-N .'-alkyl-N ¹ -arylthioureas and their use as herbicides.

The ureas active as herbicides according to the invention correspond to the formula

(ι) " (Y) £ Λ 0
It
-NH-C-Nc; E. η = / ■ in which

E alkyl with about 1 to 4 carbon atoms,

Y halogen having an atomic number of 9 to 35, i.

F, Cl or Br, or alkyl or alkoxy with 1 to

about 4 carbon atoms, ■ η either O or an integer from 1 to 3

909Ö37 / 1S9 2

. (when Y is halogen) or 1 (when Y

Represents alkyl or alkoxy), ν --..-- "" - Z Halogen with an atomic number of 9 to 35

or alkyl of 1 to about 4 carbon

atoms and
a either 0 or an integer from 1 -

5 (when Z is halogen) or 1 (when Y

Alkyl is).

The Y · and Z 'groups, in which K and a denote numbers above 1, can be identical or different, but are preferably the same. Preferably, the compounds are used in which E is methyl or ethyl, η either O or 1 (where Y is Cl, Br 1, methyl or methoxy) or 2 (where Y is Ol or Br) and a is either 0 or 1 (where Z is methyl or Gl) or 5 (where Z is Cl). represents. ,; ;

Examples of ureas corresponding to formula (l) ^, are: :

if-m-bromophenyl-W-methyl-F ¹ -phenylthio-, Hp-fluorophenyl-ii'-methyl-I \ T '-p-chlorophenyl thio-, 1-2,5-dibromophenyl-li-methyl - !! '- p-tromphenylthio-, N - ^ - bromo-S-chlorophenyl-N'-isopropyl- ' - \ N'-phenylthio-, N-2,4,6-trichlorophenyl-B '' - ethyl- Ä ^T '-2,5-dichlorophenylthio-, F-3j4-difluorophenyl-N ^l -methyl-li'-p-fluorophenylthio-, Fm-A'thylphenyl-H' -methyl-N -3,4-dibromophenylthio- , IT-p-Cumyl-li ^ -n-butyl-Jiif-p-chlorophenylthio-, Hp- · - "'.-. Butylphenyl-I \ T'-methyl -Ή ' -pentachlorophenylthio-, l \ fo-ethpxyphenyl -N'-methyl-JSr'-tolylthio- ", Hp-Butoxyphenyl-I \ r '-. Ethyl-Ii' -p-chlorophenylthio-, Ή-2 , 4,6-tribromophenyl-H · propyl-H ' -pcumylthio-, Wp-ethylphenyl-l '-butyl-Ut-p-butylphehylthio- ,. ii-p-Äthoxyphenyl-li'-ethyl-N'-2,4,6-trichlorophenyl thio-, ir-pa? olyl-N -mithyl-U '-pentabromophenylthio-, Np-tolyl-H''methyl - Ή '-3,4-difluorophenylthio- and Np-methoxyphehyl-ir' propyl-H "'- 2 _r 4,6-trifluorophenyl thiourea _.:

The above-mentioned ureas can be produced by mixing a urea with a sulfenyl halide

'900 * 3-7 / 169-2

following equation

'■ ■. P ■

f Λ> -NH-C-NHR + XS- ({ \> - ■} (1), + HX

reacted, where X is halogen, preferably chlorine, and Y, R, Z -, - η and a have the meanings already given. This reaction can be carried out in dimethylformamide or pyridine with or without an acid acceptor or in other solvents such as methylene chloride, chloroform, acetonitrile or dimethoxyethane using an acid acceptor. Acid acceptors which can be used together with dimethylformamide and the other solvents mentioned are pyridine, ' Alkylpyridines, quinoline and corresponding heterocyclic bases. Pyridine is preferably used as "acid acceptor". Pyridine is used alone, so it acts both as a solvent and as an acid acceptor _c The preferred medium for carrying out the reaction consists of dimethylformamide using pyridine as an acid acceptor.

The pressures and temperatures at which the reaction is carried out are not critical. Since the reaction is exothermic .Easy, temperatures between ambient 'are temperature and about 60 ⁰ C normal. If necessary, however, it is also possible to work at lower or higher temperatures, the latter being able to extend to the decomposition temperature of the reaction participants and of the product formed. For the sake of simplicity, the reaction is carried out at atmospheric pressure or autogenous pressure. Generally, the reaction is complete within 30 minutes to "4 hours.

The urea used as starting material according to the above equation can be prepared in situ or separately beforehand

9 09837 / 1S92

will. For the production of this reaction part hehmers can common methods, e.g. the reaction of an amine with a Isocyanate.

The following examples serve to further explain the Invention. As far as stated in the examples are, it is weight percent.

example 1

A mixture of 25 g of Hp-chlorophenyl-N'-methylurea and 200 g of pyridine was placed in a flask. Then 40 g of p-chlorophenylsulfenyl chloride were added to the mixture. The combined mixture was stirred for one hour at ambient temperature. At the end of this time the mixture was added to another mixture of 200 g of concentrated HCl in one liter of ice water. The organic substance in the mixture was extracted with 500 g of methylene chloride. The extract was washed with dilute HCl, saturated I \ TaHCO, solution and water, dried and evaporated, so that an orange-colored oil was obtained, which slowly crystallized. The solid substance was recrystallized from a mixture of 50 ml of benzene and 100 ml of hexane. The recrystallized product was washed with 50 ml of hexane. In this way, 21.6 g of Up-ChI or phenyl-IT'-methyl -Ii ¹ -p-chlorophenylthiourea were obtained. The melting point of the substance was 94-97 ° C; . ■ ■ - ■■■ · ■■■■ -

Example 2

25 g of IT-p-chlorophenyl-I'-methylurea, 100 g of dimethylformamide and 11.8 g of pyridine were mixed in a flask at ambient temperature. To this mixture was added 26.6 g of p-chlorophenylsulfenyl chloride. The temperature of the mixture increased somewhat during the addition, but did not exceed 40 ^° C. The combined mixture was then stirred for one hour at ambient temperature. After this time, 1 liter of ice water was added, whereupon a solid

909837/1592

The mixture was filtered and the solid substance was washed with water and hexane and air-dried. The dried solid substance had a weight of 39 g. Gas-liquid chromatography could show that the solid Substance consisted of practically pure! -P-chlorophenyl-lf'-methyl-N'-p-chlorophenylthiourea. The melting point of the compound was 85 96 ⁰ G
on:

96 ⁰ G; the compound had the following sulfur and chlorine values

calculated: S: $ 9.80; Cl: $ 21.80 found: 'S: 9.99% Cl: 21 ,:

This compound was purified by recrystallization from benzene and hexane. The purified compound had a melting point of 95-98 ⁰ C.

Other ureas according to the invention were also used using one or more of those described above Methods made. These compounds are listed in Table I.

90983 771502

co ο co

cn cio

link

U-2,5-dichlorophenyl-1-methyl-N 'phenylthiourea

U-2,5-Eichiorphenyl-U'-methyl-U'p-Chlorophenylthiourea

IT-p-Tolyl-lir · -methyl-U '-phenylthiourea

.-Ή ¹ -methyl-li '-ρέ · ■ thiourea

"] Jr-m-chlorophenyl ~ B" '-methyl-N' -phenyltliiolarea,

U-p-Me tnoxyphenyl -U '-metliyl-lii' -plienylt-urea

■ N-p-methoxyphenyl-I-methyl-ίί '-pciilorpiienyltliiourea '. -

: U-3,4-dichlorophenyl-N '-me tiiyl-li «-, phenylthiourea

U-3,4-dichloroplienyl-N'-ethyl-I «-, phenylthiourea

Γ 9 table.1 s found Elemental analysis
Cl CfOi T _# . I. J ¹ . ) CD 8th 9.76 ■ ■] ■ 21, 62 '59 ( ⁰ C 61 O Γ 11th ffier. 9.21 21 28, 82 125 - 128 CO
O 10 , 78 11.68 29 9, 98 65 - 68 10 , 86 10.68 10 12, 25th 72 - r
75 <*
1 11th , 75 10.95; 11th 12, 28 64 - 67 9 , 4 11.08 12th 53 - 55.5 9 »9 10.18 11 42 85 - 87 9 , 10 9.92 n 21, 102 - 105 , 92 9.52 21 20, 32 51 - -55 ■ '■■■ » ⁷⁸ . ^; 20th , 5 , 39 Ber. ..65. , 45 , 3 , 57 ,1 , 00 , 7 > ⁸

Table I (Ports.)

co ο cr> σ>

cn co K>

link

ii-p-Chlorophenyl-ltf'-methyl-H'-phenylthiourea

Έ-3 , 4-Di chlorophenyl-ii'-ethyl-N · -pchlorphenylthiourea

E-m-chlorophenyl-ST'-methyl-N'-ptolylthiourea

U-phenyl-iJ * -methyl-H '-p-chlorophenylthiourea

JS-p-chlorophenyl-U '-ethyl-H "· -p-chlorophenylthiourea

IT-Phenyl-E'-methyl-U '-ρ-tolyl thiourea

li-o-Chlorphenyi-II-methyl-U '-pchlorophenylthiourea :

U-3,4_Dichlorphenyl-li'-methyl-U ^f -ptolyl thiourea.

lp-chlorophenyl-li'-methyl-U'-p- ■ tolylthiourea elemental analysis Cl ■

Ber. fief. Ber. fief. ( 74 π ^ I. 10.85 10.92 12.1 11.72 85 - 78 8.51 8.57 28.2 27.65 66 - 86.5 10.4 10.13 11.6 12.32 65 - 69 1o, 9 10.77 12.1 12.30 61 - 70 «Μ!
CD
CD 9.4 9.80. im, W β ^ J Vy 21.62 70 - 64 CD
CD 11.75 11.52 10.26 10.52 ' t-
. 79 - 75 9.80. 10.15 21.65 21.68 ■■ ⁹ ' ⁵ - 83 9.58 9.23 ■ 20.8 20.52 101 - '97 10.4 10.62, 11.55 11.78 - 103

Table I (cont.)

/ Connection ^:

NHn-chlorophenyl-F '-methyl-N' -p-chloro- / phenylthiourea

^ ply clilorpiieixyltiiibiia.rristoff I-phenyl-f '-methyl-N'-phenylthio-, urea

U-m-tolyl-II'-methyl-U-phenyltilioiiarnstoff

Nm-Tolyl-H "'-methyl-ΙΓ ^f -p ~ chl orplienylthiourea

-ir '-phenyl th.i ο-

Ef-p-bromophenyl-li '~ urea

l-p ~ bromophenyl-N'-methyl-1'-p-chlorophenylthiourea

Ber «,

8.86 ■ 8.86

12.3 12.1

11.75 11.50

10.42 9.93

9.5 ' _: 9.51

8.61 '8.43 ^:

li-3,4-dichlorophenyl-ST'-methyl-Si'-pentachlor-:. ■:.

phenylthiourea. 6 _f 41 "- _'6.11:;

Elemental analysis

. σι ■ :. .p .: ¹

Ber «gef. ':( Q)

29.45 29.50

11.55 ■: 11.52.

"749.8: ..., 49.3

9.80 9.81, 21.65 '21.82 '68 -71

100 - 102 I.
co 59 - 63 ' • 180 - 183. ■■■ 164 - 167 97 '- " ¹⁰² · 108 V Ul Y-] CD 159 -162:; O I. ' '-'; ,, ';/''■''^;'

The ureas according to the invention are in general herbicides, the _β · can be applied both before and after emergence of the plants in order to prevent of absorption of unwanted Pflanzenwuehs are the ureas in sufficient quantity to the appropriate environment, for example on the floors, ¹ In containing seeds and / or seedlings of such plants are applied. When the ureas are used in this way, growth is prevented and the seeds, the germinated seeds and the plants that have just emerged are killed. When the compounds are used after the plants have emerged, they are applied directly to the leaves or other parts of the plants. The compounds are effective against both weed grasses and broad-leaved weeds.

Typical ureas according to the invention were made according to the following Methods for their effectiveness as herbicides when applied before and after the rising. Plants checked? · ■

Test before .. the plants emerge

An acetone solution of the test compound was prepared by one 750 mg of urea, 220 mg of a surfactant and 5 ml of acetone mixed. This solution became approximately 125 ml Added to water containing 156 mg of a surfactant. Seeds' of a test plant were placed in a pot with Soil planted, whereupon the urea solution evenly on the soil surface was sprayed in an amount

of 200 micrograms per cm. The pot was poured and placed in a greenhouse. The pot ^: was poured at intervals and on the sprouting of the seeds, the health of the. germinating seeds uswo watched over a 5 week period. At the end of this period, the herbicidal activity of the urea was determined according to the physiological observations. A rating scale from 0 to 100 was used; 0 means no phytotoxicity j 100 means complete destruction _e

9098 37/159

- to -,.-19.Ί Q-49.Ö ""

Check after the plants have opened.

The solution with the urea to be tested was carried out in the same way as described in the "Test before the emergence of the plants". The urea concentration in this approach was 5000 parts per million. This approach . '.-Was uniformly about 2, corresponding pots 24-day-old test plants (about 15 - 25 plants per _tonne pot) was sprayed, in an amount of 100 micrograms / fcm ₀ JJachdem the plants had dried, the pots were placed in a greenhouse set. The plants were watered at intervals at the bottom (if necessary) and periodically for phytotoxic, physiological and morphological effects. The response of the treatment considered, after 5 weeks the herbicidal effect of the urea was assessed on the basis of the observations made. Again, a rating scale from 0 to 100 was used; 0 means no phytotoxicity; 100 means complete annihilation *

The results of the tests are summarized in Table II below. For comparison, structurally related compounds, namely Fp-chlorophenylthio-li ^l -p-chlorophenylurea, li, W_Dimethyl-H "-p-chlorophenylthiourea and U-methyl-U'-p-chlorophenylthiourea" were used and also tested according to the above method. The results of these tests are also included in Table II.

GD

Strnjnx ^ jcsp 'jaq _rao / imaB.iSoj: is [Ti Ό01- i

οοτ / 66 οοτ / οοτ οοτ / οοτ οοτ / οοτ

οοτ / οοτ οοτ / οοτ

οοτ / οοτ οοτ / οοτ οοτ / οοτ bl / οοτ qL ^: / οοτ., ql / 96 , 09/96

οοτ / οοτ οοτ / σοτ οοτ / οοτ ·. οοτ / οοτ οοτ / οοτ οοτ / οοτ οοτ / 66

ι, ■ ■ ■ ■. ■. · '... ■

r U οοτ / οοτ οοτ / οοτ οοτ / οοτ οοτ / οοτ οοτ / οοτ οοτ / οοτ

οοτ / οοτ οοτ / οοτ οοτ / οοτ. οοτ / οοτ οοτ / οοτ οοτ / οοτ οοτ / οοτ

οοτ / οοτ οοτ / οοτ οοτ / οοτ οοτ / οοτ "οοτ / οοτ οοτ / οοτ οοτ / οοτ

οοτ / οοτ οοτ / οοτ οοτ / οοτ οοτ / οοτ, οοτ / οοτ «οοτ / οοτή 96/96; ';

■ ■ ·. &:;'s 2} j jo q. STiJCBt [O τ

, K

Jj ^

»Κ-χϋ ^ Γί-θΐπ-, H-iiC.iisqdJCOxt [p-ni-jj

j j ο q. strJBtrö Tttq. x ^ ttetrdJi: ο χ-qo

CO CD O O)

am-, no- x ^

-g * g-j

Table II (Ports.)

-3,4-DiClIlOrPiIeIIyI-Ii ¹ -äth.yl-

»Nltiö

Itf-p-chlorophenyl-i \ i-methyl-Itf 'plienylthiourea

üj-m-Giilorplienyl-lM '-metliyl_I' p-tolylthiourea

IT-Phenyl-H '-p-chlorophenylthio- Έ ♦ -methylurestοff

iY-p-chlorophenyl-ϊί '-ethyl-ϊΓ' p-c-morphenyltMoiiarnstoff

-Sr -p-

tJiioiiamstoff

p-tolyl-

Uo-Clilorph.enyl-li'-methyl -Ή 'p-chlorpiLenyltMoliams t of f

Έ-3't 4-DiChIOrPiLeIIyI-H '-methyl-Ii'-p-tolylthiourea ^

Herbicidal effect before / after emergence

78 / iO'O lOÖ / lOO lOO / lOÖ ■ ■ lOü / lOO, lOO / lOO 100/100 iOO / 100

100/100 100/100 100/100 100 / 100'100 / 100 10 ^ / iOü 100 / Ίθυ

100/100 100/100 100/100 Ιθυ / 100 lOO / lOO 100/100 lOO / lÖO

100/100 100/100 100/100 100/100 100/100 lOO / lÖO lOÖ / loO

. '■■■■, ■'. ■ ■ _i

'. ■■ ■ '.. ■' ■■ '..' ■ '. ■' ■■ '^

90/60 10Ü / 78 100/60 10 ^ / 78 · 1Ö0 / 96 100/96 '100/96 »

100/100 100/100 100/100 100/100 100/100 100/100 100/100

100 / - 100 / - 100 / - 100 / - .100 / 78 .100 / 7.8, 100/100 l-OOAOO-iOO / lOO- 100/100 -100/100 άΟΟ / ίΟΟ 100/100

cn "■ ■ ■■ ■ '". · '' '■■ ■. ■. : ■■ ■ ■ ■ ■. ,.

O ■ '''. . ■■■ ■ ' ■■■ ■''. - ■■■ '■ ■; .. ".. ■ ■''■

σ> '. ■ ■. '■''' ■■, ■■ '■ ■' ■ ■ ■ ', ^; , '■,, ■' V .. "

r- οοτ / οοτ οοτ / οοτ οοτ / οοτ οοτ / οοτ οοτ / - 06 / οοτ οβ / οοτ

οοτ / οοτ οοτ / οοτ οοτ / οοτ οοτ / οοτ οοτ / - ^ οοτ / οοτ οοτ / οοτ

. οοτ / οοτ οοτ / οοτ οοτ / οοτ ορτ / όοτ οοτ / - 8 /, / οοτ οοτ / 9β

οοτ / οοτ οοτ / οοτ οοτ / οοτ οοτ / οοτ οοτ / σοτ οοτ / οοτ οοτ / οοτ qq

^ οοτ / οοτ οοτ / οοτ "οοτ / οοτ οοτ / ορτ · οοτ / οοτ οοτ / οοτ ορτ / οοτ

οοτ / οοτ οοτ / οοτ οοτ / οοτ οοτ / οοτ οοτ / οοτ. ' οοτ / οοτ οοτ / οοτ jjoq.s. ■ <* »

—Xiar-Btni ^ trq. oxo: -, jü— ο Ttiq.T ^ ti9t [da: orE [o °°

οοτ / οοτ οοτ / οοτ 'οοτ / οοτ οοτ / οοτ οοτ / οοτ οοτ / οοτ οοτ / οοτ ΟΟτ / ΟΟτ ΟΟτ / _ΟΟτ ο οτ / οθτ 96 / θ6 09/82, Οθτ796 Οθτ / 96

* -1 JSE-T-AtrsTTdjeoΊΠϊΟτ ^ "J

3, K Ά O Ή. . O rasp

II

Table II (cont.)

Connection .

ppy-lT ^f -pchl ο rph enylharns t ο ff

Ii, Ii · -Dimethyl-I-p-chi ο rphenylthiourea

H-me thyl-ii'-p-chi ο rpheny.1 thi ohurea

Q = Yiiildhafer (Avena fatua)

Έ, ~ annual Jaargräs (Lolium multiflorum)

C ~ foxglove (Digitaria sanguinalis) ,,

W = water grass (Bohinochloa crusgalli)

M ~ mustard (Brassioö. Arvensis)

ϊ * = Puchsschwana (Aaaranthus retroflexus),

Ji SB Melde (Chenppodium album) ■ ■■. ,: ■ ι ■

O E ■■ 0 0/0 0/0 Herbicidal effect
vö.r / after. de, m rise
MP ■ 0/0 L. 0/0 0/0 0/5 0/0 Comparison attempts 0/0. 0/0 0/0 0/0 o / o 0/0 0/0 0/5 0/5 0/0 0/0 0/0 0/0 o / o i '

■ f> " CD

The amount of urea that has to be applied varies depending on the part of the plant to be treated or the plant growth medium to be treated, the type of area to be treated, ie whether it is protected areas such as greenhouses or to free areas such as: fields, as well as of the desired type of control. For a pre-emergence control, dosages between about 0.23 to 9.1 kg per 4000 square meters are sufficient for most plants. An application at this level gives a concentration of about 2 to 80 parts per million urea divided into 0.1.2 m. For use after the plants have emerged, for example for spraying leaves, preparations are suitable which ^{contain about 0.23 to 3.6 kg of urea to 379:} 1 spray solution. This application corresponds to about 0.23 to 9.1 kg of urea per 4000 m ² . . ^? ''"?'

The herbicidal preparations according to the invention consist of: * an effective amount of one or more of the ^! ureas described above in an intimate mixture with a biologically inert carrier material. The carrier material can be a liquid diluent such as water or acetone or a solid substance. The solid substance can be in the form of dusts, powders, or granules. The preparations generally also contain other additives, such as acidic agents or dispersants, which facilitate penetration into the growth medium of the plants or the plant tissue and generally increase the effectiveness. The preparations can also contain other pesticides, stabilizers, conditioning agents, fillers U-. Ä.; contain. ; \

90 983 7 / IS

Claims (1)

Claims - in which Pl alkyl with about. 1 to 4 'carbon atoms, Y "halogen with an atomic number of 9 to 35,. Alkyl or alkoxy each with 1 to about 4 Carbon atoms,. '■■ η etrfcweder O or a whole number from 1 to 5- - if Y is halogen - or 1 - "if - Y is ATiiyl - - or alkoxy -, '/ Z halogen with an atomic number of 9 Ms 35 or more Alkyl having from 1 to about 4 carbon atoms and a either 0 or an integer from 1 to 5 - when Z is halogen - or 1 - when Y is alkyl is, _ .- ■ "". . "■ .." ■ "■ '- ■ -" ■ ■ mean. Urea derivatives enjoy claim 1, characterized in that R-ITethy 1 or ethyl, η either O or 1- if T Eq. Represents Br, methyl or hethoxy - or 2 _; .- v / enn Y Gl, or Br is - and a is either O or 1 --- v / enn. S represents methyl or Gl - or 5 - v / ean Z is Cl - means / -. Weed control agents that can be applied to the weeds as well as to the animal growth medium ^: characterized in that it consists of a sufficient amount of a urea derivative according to claim 1 in a mixture with a biologically inert carrier material, '* . Ancestors for the control of undesirable 2 lances / growth, 809037 / Tfti BAD .QRiQiNAt 1310480 by pointing to the plants acle ^ On.D an axis-reaching henge of a urea dorivatos according to spoke 1 oäqr 2 applies. Clievron Research y San Pxanclsco, OaI * _r "V., Q Eeciitsanvratt ^ """·' ^: -' ^/? 'BAD ORIGINAL