WO1981002156A1 - Procede de preparation de derives de n-aryle-n'-uree mono ou disubstitues - Google Patents

Procede de preparation de derives de n-aryle-n'-uree mono ou disubstitues Download PDF

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Publication number
WO1981002156A1
WO1981002156A1 PCT/HU1981/000003 HU8100003W WO8102156A1 WO 1981002156 A1 WO1981002156 A1 WO 1981002156A1 HU 8100003 W HU8100003 W HU 8100003W WO 8102156 A1 WO8102156 A1 WO 8102156A1
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WO
WIPO (PCT)
Prior art keywords
general formula
aryl
urea
group
mixture
Prior art date
Application number
PCT/HU1981/000003
Other languages
English (en)
Inventor
L Voeroeshazy
S Toeroek
I Daroczi
P Galambos
Z Oermenyi
Original Assignee
Reanal Finomvegyszergyar
L Voeroeshazy
S Toeroek
I Daroczi
P Galambos
Z Oermenyi
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from HU15880A external-priority patent/HU185613B/hu
Priority claimed from HU15780A external-priority patent/HU184715B/hu
Application filed by Reanal Finomvegyszergyar, L Voeroeshazy, S Toeroek, I Daroczi, P Galambos, Z Oermenyi filed Critical Reanal Finomvegyszergyar
Priority to BR8106184A priority Critical patent/BR8106184A/pt
Priority to AT900681A priority patent/AT379146B/de
Priority to AU67079/81A priority patent/AU6707981A/en
Priority to DE19813133794 priority patent/DE3133794A1/de
Publication of WO1981002156A1 publication Critical patent/WO1981002156A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/36—Radicals substituted by singly-bound nitrogen atoms
    • C07D213/40—Acylated substituent nitrogen atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C273/00—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
    • C07C273/18—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of substituted ureas
    • C07C273/1809—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of substituted ureas with formation of the N-C(O)-N moiety
    • C07C273/1836—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of substituted ureas with formation of the N-C(O)-N moiety from derivatives of carbamic acid
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/16—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms
    • C07D295/20—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms by radicals derived from carbonic acid, or sulfur or nitrogen analogues thereof
    • C07D295/215—Radicals derived from nitrogen analogues of carbonic acid

Definitions

  • the invention rela tes to a new process for the preparation of N-aryl- (mono- or disubstituted) -urea derivatives having the general formula ( I) ,
  • Aryl is an optionally substituted phenyl group
  • R 1 and R 2 each stand for an optionally substituted alkyl, cycloalkyl, alkoxy or phenyl group, or
  • R 1 and R 2 may form, together with the adjacent nitrogen atom, a nitrogen-containing heterocyclic group which may contain a further hetero atom, or one of R 1 and R 2 may also stand for hydrogen, with the proviso that if one of R 1 and R 2 is an optionally substituted phenyl group, the other may represent only hydrogen atom or an optionally substituted alkyl or alkoxy group.
  • the phenyl group represented by "Aryl” may bear as optional substituents preferably one or more halogen atoms, nitro group(s), lower alkyl group(s), lower alkoxy group(s), trihalo-lower alkyl group(s), lower alkylthio group(s) or a phenoxy group optionally substituted with the groups, listed in this paragraph.
  • R 1 and R 2 may represent as alkyl or alkozy group preferably a group of 1 to 4 carbon atoms, whereas the cycloalkyl groups represented by R 1 or R 2 contain prefer ably 5 to 8 carbon atoms. These groups may bear optionally e.g. the following substituents: hydroxy group, carboxy group, alkyl group, alkenyl group, alkynyl group, alkoxy group, phenyl group, substituted phenyl group or heteroaryl group. Of the nitrogen-containing heterocyclic groups represented by R 1 R 2 N- the morpholino group is preferred.
  • the compounds of the general formula (I) are biologically active or can be converted into biologically active substances.
  • Preferred representa tives of the compounds having the general formula (I) are as follows : N- phenyl-N' ,N'-dimethyl-urea (fenuron) , a herbicidal substance ,
  • N-phenyl-N -( 2-me thylcyclohexyl) -urea ( siduron) , a herbicidal substance , N-(4-chlorophenyl)-N',N'-dimethyl-urea (monuron), a herbicidal substance,
  • N-(4 -chlorophenyl)-N'-methyl-N'-methoxy-urea (monolin uron), a herbicidal substance
  • N-(4-chlorophenyl)-N' -(3-trifluoromethyl-4-chloro ⁇ henyl) urea (cloflucarban), an antiseptic agent.
  • the isocyanates applied as starting substances in the above methods are prepared generally by reacting the appropriate amines with phosgene or by subjecting the appropriate carbamates or urea derivatives to thermal decomposition (see Houben-Weyl: Methoden der organischen Chemie; Georg Thieme Verlag, Stuttgart, 1952, Vol. VIII, pp. 119-128). It is well known that phosgene is highly detrimental to health, thus reactions utilizing phosgene should be performed under keeping specific security measures. It is a further disadvantage that the reaction involves the formation of hydrochloric acid in great amounts, which is difficult to remove and causes serious corrosion problems. The methods of preparing isocyanates by thermal decomposition are very expensive because of their high demands on material and energy.
  • isocyanates applied as starting materials in the synthesis of the urea derivatives of the general formula (I), is cumbersome, sophisticated and expensive, and the reaction cannot be performed economically on industrial scale. It is a further disadvantage that isocyanates, owing to their high reactivity, are instable compounds and can be stored for a limited period, sometimes for some days only. Thus e.g. 4-nitrophenyl- isocyanate undergoes water addition and subsequent condensation upon storage, whereby dimers, trimers and other oligomers are formed which cannot be reacted with amines in the subsequent step (see Houben-Weyl: Methoden der organischen Chemie, Georg Thieme Verlag, Stuttgart, 1952, Vol. VIII, p. 159).
  • urea derivatives can be prepared by reacting carbamates with appropriate primary or secondary amines in the presence of a tertiary amine catalysts see e.g. J. Am. Chem. Soc. 76, 4458-4463 (1954) . According to the literature, however, only phenyl carbamates and substituted phenyl carbamates are reactive enough (Houben-Weyl: Methoden der organischen Chemie, Georg Thieme Verlag, Stuttgart, 1952, Vol. VIII, pp.
  • the invention aims at the elaboration of a new method for the preparation of urea derivatives having the general formula (I), which requires easily available starting substances, provides the end-products with high yields within a short time, and does not apply substances detrimental to health.
  • the invention is based on the recognition that lower alkyl carbamates can be converted into the respect ive urea derivatives directly, i.e. without converting them first into isocyanates, within a short time and with high yields if they are reacted with the respective amines in the presence of higher tertiary alklylamine catalysts instead of the lower tertiary amines (most frequently triethylamine or pyridine) utilized so far. It has also been observed that if phenyl or substituted phenyl carbamates are applied as starting substances in the above reaction and the lower tertiary amine catalyst is replaced by a higher tertiary alkylamine, the required end-products are obtained with higher yields.
  • N- (4-cyanophenyl)-N' -(3-pyridylmethyl)-urea can be obtained with a yield of 85 to 90% instead of 43 % attained when operating as described in Example 2 of the Hungarian patent specification 1.0. 168,295.
  • the invention relates to a new method of preparing an urea derivative of the general formula (I),
  • Aryl - NH - CO - X (IV) R 1 R 2 NH (V) wherein R 1 , R 2 and Aryl are as defined above and X is a lower alkoxy, phenoxy or substituted phenoxy group, in the presence of a tertiary amine catalyst.
  • a tertiary alkylamine containing altogether at least 6 carbon atoms and minimum one alkyl chain with at least 4 carbon atoms or a mixture of such tertiary alkylamines is applied as catalyst.
  • di (C 1- 3 alkyl) -butylamines can also be applied as tertiary alkylamine catalysts, it is more preferred, however, to perform the reaction in the presence of a tertiary amine wherein the highest alkyl chain contains a t least 8, particularly at least 12 carbon atoms.
  • the other two alkyl groups attached to the nitrogen atom may be lower alkyl groups, such as methyl or ethyl group.
  • the tertiary alkylamine catalysts the following compounds are particularl preferred: trioctylamine , N,N -dimethyl-n-octylamine , N, N -dime thyl-n-dodecylamine , N,N -dimethyl-n-hexadecyl- amine and the respective N,N -diethyl or N-methyl-N -ethyl compounds. These substances are easily available on the marke t.
  • mixtures of higher tertiary alkylamines can also be applied as catalysts in the process of the invention. From economical aspects it is pre ferred to utilize such mixtures of technical quality in large-scale operations, since these mixtures are far less expensive than the pure tertiary amines without any appreciable decrease in their catalytic activity.
  • mixtures of higher tertiary alkylamines e.g. the products sold by the firm Hoechst A.G. under the trade name "Genamin” as well as those sold by the firm Akzo under the trade name "Armeens" are to be mentioned.
  • substituent X refers to C 1- 4 alkoxy groups, such as methoxy, ethoxy, etc.
  • substituted phenoxy used in connection with group X refers to phenoxy groups which bear one or more substituent(s) inert under the reaction conditions, such as halogen atoms or alkyl, alkoxy, trihaloalkyl and/or nitro groups.
  • substituents attached to the phenoxy group are electron-attracting groups (e.g. halogen atoms, nitro group), since the phenoxycarbamates with electron-attracting substituents on the aromatic ring are particularly reactive under the conditions according to the invention.
  • the lower alkyl carbamates regarded so far as substances which cannot be used for the direct industrial preparation of urea derivatives, can be converted directly into the respective ureas within some hours generally with yields of
  • phenoxy or substituted phenoxy carbamates are applied as starting substances, the end-product may be obtained with almost quantitative yields in a fast reaction.
  • the starting substances i.e. the carbamates and the primary or secondary amines
  • the higher tertiary alkylamine catalyst is added to the mixture in an amount of 0.05 to 2 moles, preferably 0.5 to 1.2 moles, calculated for 1 mole of the starting substance present in the lower molar amount.
  • Tfhen a mixture of higher tertiary amines is applied as catalyst, this ratio relates to the total amount of tertiary amines.
  • the reaction is performed generally in an inert solvent medium, such as benzene, toluene or xylene, preferably under boiling the reaction mixture.
  • an inert solvent medium such as benzene, toluene or xylene
  • the excess of the higher tertiary alkylamine may also serve as solvent, or sometimes the reaction may also be performed in the absence of solvent or diluent.
  • the urea derivatives of the general formula (I) are generally sparingly soluble in the reaction medium and separate as solids upon cooling the mixture. In such instances the end-products can be separated easily by filtration or centrifugetion.
  • the resulting mother liquor which contains solvent, higher tertiary alkylamine catalyst, minor amounts of unreacted starting substances and dissolved end-product, can be utilized repeatedly as reaction medium for further reaction steps. Thereby the specific demand on reactants and catalyst can be decreased substantially. In such instances it is preferred to apply the starting substances in equimolar ratio in order to avoid the accumulation of one of the reactants in the mixture. V/hen the mother liquor is recycled the yield generally increases, since after the first step no further losses arise owing to the dissolution of the end-product.
  • the end-products which do not precipitate from the reaction mixture upon cooling can be separated from the mixture by known methods, such as evaporation, precipitation with non-solvents, etc.
  • agrochemical compositions such as spray solutions, impregnated granules, etc.
  • the mother liquors obtained after the separation of the solid end roducts, which contain certain amount of dissolved urea derivatives, can also be applied for the same purpose.
  • the separated crude urea derivatives can be applied either as such or after purification.
  • the process of the invention can equally be applied for the preparation of symmetrically and asymmetrically substituted urea derivatives.
  • Example 1 The layer chromatographic analyses referred to in the examples were performed on Merck Eieselgel 60 F254. plates. The melting points are uncorrected values.
  • Example 1 The layer chromatographic analyses referred to in the examples were performed on Merck Eieselgel 60 F254. plates. The melting points are uncorrected values.
  • Example 6 One proceeds as described in Example 6 with the difference that a distiliating column is attached to the flask, the mixture is maintained in gentle boiling and methanol is removed continuously from the mixture. After 2 hours of reaction the end-product is filtered off, 50 mmoles of methyl N-(4-nitrophenyl)-carbamate and 50 mmoles of 4-nitroaniline are added to the filtrate, and the reaction is repeated.
  • Table 2 The results of four subsequent cycles are summarized in Table 2. Remark:. The quality of the end-product cannot be characterized appropriately on the basis of its melting point, since the compound starts to sublime directly after melting.
  • Example 11 One proceeds as described in Example 11 with the difference that 100 ml of xylene are applied as solvent, and the progress of the reaction is monitored by layer chroma tography. When the reaction has proceeded to about 90 %, as indicated by the chroma togram, the mixture is evaporated in vacuo. A yellowish, viscous residue is obtained, which is well soluble in common organic solvents, such as acetone or methyl-ethyl ketone, and can be applied in the preparation of a herbicidal spray solution.
  • N -(4-chlorophenyl) -N', N'-dimethyl-urea monuron
  • a solution of N -(4-chlorophenyl) -N', N'-dimethyl-urea ( monuron) is obtained, which can be applied directly in the preparation of herbicidal compositions , such as spray liquids or impregnated granules.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

Nouveau procede de preparation de derives de N-aryle-N -uree mono ou disubstitues possedant la formule generale (I), (FORMULE) dans laquelle aryle est un groupe phenyle facultativement substitue, et R1 et R2 representent chacun un x groupe alkyle, cycloalkyle, alcoxy ou phenyle, ou R1 et R2 peuvent former, en combinaison avec l'atome d'azote adjacent, un groupe heterocyclique azote pouvant contenir un hetero atome supplementaire, ou un des groupes R1 et R2 peut aussi representer de l'hydrogene, a condition que si l'un des groupes R1 et R2 est un groupe phenyle facultativement substitue, l'autre peut representer seulement un atome d'hydrogene ou un groupe alkyle ou alcoxy facultativement substitue, en faisant reagir un carbamate de la formule generale (II) avec une amine de la formule generale (III), R1R2N-CO-X (II) Aryle-NH2 (III) ou un carbamate de formule generale (IV) avec une amine de formule generale (V), Aryle-NH-CO-X (IV) R1R2NH (V) ou R1, R2 et aryle sont definis comme ci-dessus et X est un groupe inferieur alcoxy, phenoxy ou phenoxy substitue, en presence d'un catalyseur amine tertiaire, Selon l'invention une alkylamine tertiaire contenant dans l'ensemble au moins six atomes de carbone et au moins une chaine alkyle avec au moins quatre atomes de carbone ou un melange de ces alkylamines tertiaires est appliquee en tant que catalyseur.
PCT/HU1981/000003 1980-01-25 1981-01-23 Procede de preparation de derives de n-aryle-n'-uree mono ou disubstitues WO1981002156A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
BR8106184A BR8106184A (pt) 1980-01-25 1981-01-23 Processo para preparacao de derivados de n-aril-n'-(mono-ou dissubstituido)-ureia
AT900681A AT379146B (de) 1980-01-25 1981-01-23 Verfahren zur herstellung von n'-(mono- oder disubstituierten)-n-aryl-harnstoff-derivaten
AU67079/81A AU6707981A (en) 1980-01-25 1981-01-23 Process for the preparation of n-aryl-n-(mono-or
DE19813133794 DE3133794A1 (de) 1980-01-25 1981-01-23 Verfahren zur Herstellung von N'-(mono-oder disubstituierten) N-Aryl-Harnstoff-Derivaten

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
HU15880A HU185613B (en) 1980-01-25 1980-01-25 Process for preparing n-acyl-n'-/mono- or disubstituted/-carbamides
HU15780A HU184715B (en) 1980-01-25 1980-01-25 Process for the preparation of n-bracket-4-nitro-phenyl-bracket closed-n-comma above-bracket-3-pyridyl-methyl-bracket closed-urea
HU157/80 1980-01-25

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Publication Number Publication Date
WO1981002156A1 true WO1981002156A1 (fr) 1981-08-06

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US (1) US4410697A (fr)
BR (1) BR8106184A (fr)
CH (1) CH649078A5 (fr)
GB (1) GB2080808B (fr)
SU (1) SU1246891A3 (fr)
WO (1) WO1981002156A1 (fr)

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DE4028040A1 (de) * 1990-09-05 1992-03-12 Chemie Linz Deutschland Verfahren zur n-alkylierung von harnstoffen
US5099021A (en) * 1989-11-10 1992-03-24 Agrolinz Agrarchemikalien Gesellschaft M.B.H. Process for the preparation of pure, unsymmetrically disubstituted ureas
US5106873A (en) * 1990-06-26 1992-04-21 Warner-Lambert Company ACAT inhibitors
US5169954A (en) * 1990-08-14 1992-12-08 Chemie Linz Gesellschaft M.B.H. Process for the N-alkylation of ureas

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US5003106A (en) * 1983-07-19 1991-03-26 American Cyanamid Company Antiatherosclerotic ureas and thioureas
US4889589A (en) * 1986-06-26 1989-12-26 United Technologies Corporation Gaseous removal of ceramic coatings
US4797411A (en) * 1986-07-18 1989-01-10 Farmitalia Carlo Erba S.P.A. Cycloalkyl-substituted 4-pyridyl derivatives and use as aromatase inhibitors
DE3636190A1 (de) * 1986-10-24 1988-04-28 Bayer Ag Verfahren zur herstellung von n,n-diaryl-harnstoffen
US4716175A (en) * 1987-02-24 1987-12-29 Warner-Lambert Company Saturated fatty acid amides as inhibitors of acyl-CoA:cholesterol acyltransferase
US4743605A (en) * 1987-02-24 1988-05-10 Warner-Lambert Company Saturated fatty acid amides as inhibitors of acyl-coa:cholesterol acyltransferase
US5015644A (en) * 1987-06-02 1991-05-14 Warner-Lambert Company Antihyperlipidemic and antiatherosclerotic urea and carbamate compounds
US4868210A (en) * 1988-03-30 1989-09-19 Warner-Lambert Company Antihyperlipidemic and antiatherosclerotic compounds and compositions
US5116848A (en) * 1988-03-30 1992-05-26 Warner-Lambert Company N-(((2,6-disubstituted)phenyl)-n-diarylalkyl)ureas as antihyperlipidemic and antiatherosclerotic agents
FR2646847B1 (fr) * 1989-05-12 1991-07-12 Rhone Poulenc Sante N-phenyl amides, leurs procedes de preparation et les medicaments les contenant
AT397384B (de) * 1991-08-16 1994-03-25 Chemie Linz Gmbh Verfahren zur herstellung reiner n,n'-unsymmetrisch substituierter phenylharnstoffe
US5312820A (en) * 1992-07-17 1994-05-17 Merck & Co., Inc. Substituted carbamoyl and oxycarbonyl derivatives of biphenylmethylamines
US6344476B1 (en) 1997-05-23 2002-02-05 Bayer Corporation Inhibition of p38 kinase activity by aryl ureas
US6187799B1 (en) * 1997-05-23 2001-02-13 Onyx Pharmaceuticals Inhibition of raf kinase activity using aryl ureas
US7517880B2 (en) 1997-12-22 2009-04-14 Bayer Pharmaceuticals Corporation Inhibition of p38 kinase using symmetrical and unsymmetrical diphenyl ureas
US20080300281A1 (en) * 1997-12-22 2008-12-04 Jacques Dumas Inhibition of p38 Kinase Activity Using Aryl and Heteroaryl Substituted Heterocyclic Ureas
US7329670B1 (en) 1997-12-22 2008-02-12 Bayer Pharmaceuticals Corporation Inhibition of RAF kinase using aryl and heteroaryl substituted heterocyclic ureas
US20080269265A1 (en) * 1998-12-22 2008-10-30 Scott Miller Inhibition Of Raf Kinase Using Symmetrical And Unsymmetrical Substituted Diphenyl Ureas
US7928239B2 (en) 1999-01-13 2011-04-19 Bayer Healthcare Llc Inhibition of RAF kinase using quinolyl, isoquinolyl or pyridyl ureas
US7351834B1 (en) 1999-01-13 2008-04-01 Bayer Pharmaceuticals Corporation ω-Carboxyaryl substituted diphenyl ureas as raf kinase inhibitors
US8124630B2 (en) 1999-01-13 2012-02-28 Bayer Healthcare Llc ω-carboxyaryl substituted diphenyl ureas as raf kinase inhibitors
JP2002534468A (ja) 1999-01-13 2002-10-15 バイエル コーポレイション ｐ３８キナーゼ阻害剤としてのω−カルボキシアリール置換ジフェニル尿素
EP1140840B1 (fr) 1999-01-13 2006-03-22 Bayer Pharmaceuticals Corp. Diphenylurees a substituants -g(v)-carboxyaryles, inhibitrices de kinase raf
AU7353300A (en) 1999-09-08 2001-04-10 Guilford Pharmaceuticals Inc. Non-peptidic cyclophilin binding compounds and their use
US7235576B1 (en) 2001-01-12 2007-06-26 Bayer Pharmaceuticals Corporation Omega-carboxyaryl substituted diphenyl ureas as raf kinase inhibitors
JP2004532187A (ja) 2001-01-25 2004-10-21 ギルフォード ファーマシュウティカルズ インコーポレイテッド 三置換カルボサイクリックサイクロフィリン結合化合物とその用途
US7371763B2 (en) * 2001-04-20 2008-05-13 Bayer Pharmaceuticals Corporation Inhibition of raf kinase using quinolyl, isoquinolyl or pyridyl ureas
US20040023961A1 (en) * 2002-02-11 2004-02-05 Bayer Corporation Aryl ureas with raf kinase and angiogenisis inhibiting activity
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EP2324825A1 (fr) 2002-02-11 2011-05-25 Bayer Healthcare LLC Arylurées dotées d'une activité d'inhibition de l'angiogenèse
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US7557129B2 (en) 2003-02-28 2009-07-07 Bayer Healthcare Llc Cyanopyridine derivatives useful in the treatment of cancer and other disorders
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BE1026422B1 (nl) 2018-07-02 2020-02-03 Belchim Crop Prot N V Synergetisch werkzame herbicidesamenstelling omvattende metobromuron en clomazon

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5099021A (en) * 1989-11-10 1992-03-24 Agrolinz Agrarchemikalien Gesellschaft M.B.H. Process for the preparation of pure, unsymmetrically disubstituted ureas
US5106873A (en) * 1990-06-26 1992-04-21 Warner-Lambert Company ACAT inhibitors
US5169954A (en) * 1990-08-14 1992-12-08 Chemie Linz Gesellschaft M.B.H. Process for the N-alkylation of ureas
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SU1246891A3 (ru) 1986-07-23
CH649078A5 (de) 1985-04-30
GB2080808B (en) 1984-01-04
BR8106184A (pt) 1981-11-24
GB2080808A (en) 1982-02-10
US4410697A (en) 1983-10-18

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