Classifications

• • 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
  • C07D295/18—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 carboxylic acids, or sulfur or nitrogen analogues thereof
• • 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
  • C07D295/18—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 carboxylic acids, or sulfur or nitrogen analogues thereof
  • C07D295/182—Radicals derived from carboxylic acids
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
  • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
  • A01N43/84—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms six-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,4
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C231/00—Preparation of carboxylic acid amides
  • C07C231/12—Preparation of carboxylic acid amides by reactions not involving the formation of carboxamide groups

Definitions

• the invention concerns a new process for the preparation of 3,3-diaryl acrylic acid amides of the general formula I
• R- represents a C. , alkyl, C- , alkoxy, amino, mono- or di-(C- , alkyl)amino, C_ , alkenyl, C, , alkynyl, C_ , alkenyloxy, C, , alkynyloxy or C_ , cycloalkyl group;
• R_ represents a C- , alkyl or C- , alkoxy group or a halogen atom
• R_ represents a hydrogen or halogen atom
• R represents a hydrogen or halogen atom or a C. , alkyl or C- , alkoxy group
• R represents a hydrogen atom, a phenyl group optionally substituted by one or more substituents selected from C. , alkyl, C- , alkoxy, halogen, phenyl and phenoxy moieties, a C. _. spatial alkyl group optionally substituted by one or more halogen atoms, a C_ cycloalkyl group, a C sharp , alkenyl or a C. . alkynyl group each optionally substituted by a phenyl group, or a naphthyl or C.
• -X-Y- represents a single bond or a -0- , -S(0) -, -N-N- ,
• R fi represents a C. , alkyl, C, - cycloalkyl, benzyl, C, , alkenyl or C. , alk3rnyl group;
• R ? represents a C- , alkyl group
• R R represents a hydrogen atom or a C- , alkyl or C- , alkoxy group
• R q and R- fi independently represent a hydrogen atom or a C. , alkyl group.
• Compounds of formula I are fungicidally active and are particularly useful in the control of phytopathogenic fungi, especially Plasmopara viticola and Phytophthora infestans.
• Particularly preferred compounds of formula I in this respect are those in which A represents a 3,4-dimethoxyphenyl, 3-ethoxy-4- methoxyphenyl, 3-chloro-4-methoxyphenyl, 3-bromo-4-methoxyphenyl, 3-methyl-4-methoxyphenyl, 3-ethyl-4-methoxyphenyl,
• B represents 4-chlorophenyl or 4-(4-chlorophenoxy)phenyl. It is also preferred that Q represents a morpholino group.
• Especially preferred compounds of the general formula I are 3-(4-chloro- phenyl)-3-(3,4-dimethoxyphenyl) acrylic acid morpholide and 3-[4-(4-chlorophenoxy)phenyl]-3-(3,4-dimethoxyphenyl) acrylic acid morpholide.
• Compounds of the general formula I as well as processes for their preparation have been described in European patent applications EP 120 321 and EP 219 756.
• Such alcoholates react readily with the water which is produced in the course of the reaction yielding the corresponding alcohol and sodium hydroxide.
• This hydroxide together with the alcoholate, in turn cleaves base-sensitive reactants, especially the acetamide, or the desired product, often to a large extent and thus reduces the yield from the process.
• Attempts to overcome this problem involved the use of a substantial excess, generally 3-fold or even higher, of the acetamide reactant.
• European patent application EP 343 743 it has been described that the above described cleavage reaction of the acetamide compounds can be suppressed by the addition of an alkali metal mono-alkyl carbonate to the reaction mixture, thereby reducing the need for excess acetamide reactant to only a small excess, and increasing the purity of the products to nearly 100%. It will be appreciated, however that there is still a need for an improved synthesis for the compounds of the general formula I, as the base used in the process according to European patent application EP 343 743 is expensive in view of the safety measures which have to be taken during the production of the tertiary alcoholates, while also the added alkali metal mono-alkyl carbonate increases the costs of the reaction.
• the present invention therefore relates to a process for the preparation of a compound of the general formula I in which A, B and Q are defined as above, by condensing a compound of the general formula II
• Suitable alkanes and cycloalkanes for the process of the present invention are alkanes or cycloalkanes containing from 5 to 16 carbon atoms, especially alkanes or cycloalkanes containing from 6 to 12 carbon atoms or mixtures thereof.
• the alkane or cycloalkane contains 7 or 8 carbon atoms, and more preferably the alkane is n-heptane or n-octane.
• Suitable alkanes are also alkane distillation fractions with a specified boiling range.
• a suitable cycloalkane is cyclohexane.
• the process according to the invention is suitably carried out using sodium or potassium hydroxide, preferably sodium hydroxide.
• the alkali metal hydroxide is suitably used as powder. It is also possible to start with an aqueous solution of sodium hydroxide together with an organic solvent which forms an azeotrope with water, from which aqueous solution the water is removed azeotropically.
• the amount of alkali metal hydroxide is suitably between 0.1 and 3 equivalent based on starting benzophenone, preferably between 0.7 and 1.8 equivalent.
• the process according to the present invention is suitably carried out at a temperature from room temperature to the reflux temperature of the reaction mixture. Preferably the reaction temperature is between 80 ⁇ C and 160 ⁇ C, more preferably between 100 ⁇ C and 150 °C.
• the reaction time is usually between 1 and 48 hours, depending on the reaction temperature.
• the amount of acetamide in the reaction according to the present invention is suitably between 1 and 6 equivalents based on starting benzophenone compound, preferably between 1.5 and 5, more preferably between 2.0 and 4.
• the volume of solvent is suitably between a quarter of the volume of the starting products up to 100 times the volume of the starting materials, although more or less is also possible.
• the water, which is formed during the reaction is removed azeotropically from the reaction mixture.
• the water may be removed by carrying out the reaction under diminished pressure.
• Another aspect of the invention is the addition of an aromatic compound to the reaction mixture, suitably up to 60% v/v with respect to the volume of the alkane solvent, preferably up to 40 % v/v more preferably up to 20% v/v.
• Suitable aromatic compounds are toluene, xylene, mesitylene and mixtures thereof, such as commercially available mixtures of aromatics.
• Compounds of formula II and formula III are either known compounds or can be produced from known compounds by known methods. In this respect reference is made to the above cited literature citations.
• Example 1 3-(4-Chlorophenyl)-3-(3,4-dimethoxyphenyl)-acrylic acid morpholide
• Example 3 3-(4-Chlorophenyl)-3-(3,4-dimethoxyphenyl)-acrylic acid morpholide 4-Chloro-3' ,4'-dimethoxybenzophenone (27.67 g; 0.1 mol), acetyl morpholide (38.75 g; 0.3 mol) and sodium hydroxide (4.00 g; 0.1 mol) in n-octane (80 ml) were refluxed for 10 hours.
• the refluxing condensate was passed through a column packed with molecular sieves (4 A, 10 g; can be replaced by a mixture of anhydrous sodium sulphate and sea sand). Subsequently, n-octane (30 ml) was distilled off and toluene (150 ml) was added. The mixture was heated to 80°C and extracted twice with water (100 ml each) . The organic layer was separated, and dried by azeotropic distillation of a part of the solvent (70 ml) . The solution was kept at 40 ⁇ C and petrol ether (100 ml, bp.
• N-acetyl morpholine (387.6 g; 3 mol) and powdered sodium hydroxide (40.0 g; 1 mol) in n-octane (600 ml) were refluxed under stirring for 10 hours at a column internal temperature of 127°C.
• the refluxing condensate (3 1/h) was passed through a column packed with molecular sieves (4A, 150 g) .
• n-octane (450 ml) was distilled off and toluene (1 1) was added. The mixture was heated to 80°C and extracted once with 500 ml water and twice with 250 ml water.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Life Sciences & Earth Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Dentistry (AREA)
• Zoology (AREA)
• Health & Medical Sciences (AREA)
• Engineering & Computer Science (AREA)
• Pest Control & Pesticides (AREA)
• General Health & Medical Sciences (AREA)
• Wood Science & Technology (AREA)
• Plant Pathology (AREA)
• Environmental Sciences (AREA)
• Agronomy & Crop Science (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Agricultural Chemicals And Associated Chemicals (AREA)
• Cosmetics (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Priority Applications (17)

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Publications (1)

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Citations (4)

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• 1993
  • 1993-06-24 IL IL106122A patent/IL106122A/xx not_active IP Right Cessation
  • 1993-06-28 TW TW077104024A01A patent/TW271439B/zh active
  • 1993-07-08 CZ CZ955A patent/CZ282167B6/cs not_active IP Right Cessation
  • 1993-07-08 US US08/362,450 patent/US5495019A/en not_active Expired - Fee Related
  • 1993-07-08 DE DE69310369T patent/DE69310369T2/de not_active Expired - Fee Related
  • 1993-07-08 WO PCT/EP1993/001803 patent/WO1994001424A1/en not_active Ceased
  • 1993-07-08 EP EP93915866A patent/EP0649420B1/en not_active Expired - Lifetime
  • 1993-07-08 DK DK93915866.3T patent/DK0649420T3/da active
  • 1993-07-08 AU AU45672/93A patent/AU669921B2/en not_active Ceased
  • 1993-07-08 MD MD95-0234A patent/MD944G2/ro active IP Right Grant
  • 1993-07-08 PL PL93307129A patent/PL173434B1/pl unknown
  • 1993-07-08 CA CA002139736A patent/CA2139736A1/en not_active Abandoned
  • 1993-07-08 KR KR1019950700089A patent/KR100284117B1/ko not_active Expired - Fee Related
  • 1993-07-08 AT AT93915866T patent/ATE152449T1/de not_active IP Right Cessation
  • 1993-07-08 ES ES93915866T patent/ES2102662T3/es not_active Expired - Lifetime
  • 1993-07-08 NZ NZ254125A patent/NZ254125A/en unknown
  • 1993-07-08 SK SK25-95A patent/SK279604B6/sk unknown
  • 1993-07-08 BR BR9306695A patent/BR9306695A/pt not_active IP Right Cessation
  • 1993-07-08 HU HU9500053A patent/HU219133B/hu not_active IP Right Cessation
  • 1993-07-08 GE GEAP19932332A patent/GEP19981354B/en unknown
  • 1993-07-08 UA UA95028126A patent/UA41331C2/uk unknown
  • 1993-07-08 JP JP50297894A patent/JP3572073B2/ja not_active Expired - Fee Related
  • 1993-07-08 RU RU95105585A patent/RU2105762C1/ru active
  • 1993-07-09 CN CN93108160A patent/CN1035553C/zh not_active Expired - Fee Related
• 1997
  • 1997-05-30 GR GR960403253T patent/GR3023586T3/el unknown
  • 1997-07-08 TJ TJ95000029A patent/TJ163B/xx unknown

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