Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C317/00—Sulfones; Sulfoxides

Definitions

• esters of phenoxyphthalic acid are obtained when alkali metal salts or alkaline earth metal salts of hydroxyphthalic acid esters are reacted in a polar organic solvent, at temperatures of between 50 and 200 C., with derivatives of benzene which are both halogenated and substituted by electrophilic radicals.
• the end products prepared in this way may be used as molluscicides.
• the dimethyl ester of 4'-nitro-4-phenoxy-phthalic acid is particularly suitable for this purpose.
• the product of this invention can be used as plasticizers for polyvinylchloride and similar plastics.
• R and R denote any aliphatic or aromatic hydrocarbon radical which may be the same or different, and they preferably represent alkyl radicals with 1 to 6 carbon atoms. If the alkali metal salts or alkaline earth metal salts of these compounds are used in this invention, the OH group is replaced by MeO, Me denoting an alkali metal or an alkaline earth metal, preferably sodium or potassium. Examples of these compounds are dimethyl 4'hydroxyphthalate, diethyl-3-hydroxyphthalate and their sodium or potassium salts.
• R is preferably an alkyl radical having 1 to 6 carbon atoms or an aryl radical e.g. phenyl and naphthyl.
• the electron attracting radical is defined as a radical which has a s p-value according to the Hammet equation greater than 0.20.
• X is preferably in the por o-position to R
• these compounds are: p-nitrochlorobenzene, o-nitrofluorobenzene, p-cyanochlorobenzene and p- 3,686,266 Patented Aug. 22, 1972 fiuorobenzophenone; chloroand fluoronitrobenzene are particularly suitable.
• phenoxyphthalic acid esters obtained by the process according to the invention are dimethyl 4- nitro-4-phenoxy-phthalate, diethyl 2'-nitro 3 phenoxyphthalate, dimethyl 4'-cyano-4-phenoxy-phthalate and diethyl 4'-benzoyl-4-phenoxy-phthalate.
• Solvents in which the process may be carried out include organic solvents such as dimethylsulphone, dimethylsulphoxide, dimethylformamide and acetonitrile. Dimethylsulphoxide is particularly suitable.
• the process is usually carried out by first reacting a hydroxyphthalic acid ester, dissolved in an inert organic solvent such as toluene or benzene, with an aqueous alkali metal hydroxide or an alkali metal alcoholate or an alkali metal to form the corresponding alkali metal salt.
• alkali metal compounds alkaline earth metal compounds may be used. Preferably, sodium or sodium compounds are used.
• the resulting alkali metal salt or alkaline earth metal salt of the hydroxyphthalic acid ester is then reacted with the halogenated benzene in one of the aforesaid polar solvents.
• This reaction is generally carried out at 50 to 200 C.
• This stage is preferably carried out with the complete exclusion of water.
• the water formed during the reaction is distilled off azeotropically together with the organic solvent which is then returned to the reaction system after removal of the water.
• the completion of the reaction can be detected by the neutral reaction of the reaction mixture.
• the end products can be isolated from this mixture by removal, for example from the alkali metal halide or alkaline earth metal halide formed in the reaction, by filtration. The remaining solution can then be concentrated by evaporation.
• the end products prepared in this way may be used as molluscicides.
• the dimethyl ester of 4'-nitro-4-phen0xyphthalic acid is particularly suitable for this purpose.
• the products of this invention can also be used as plasticizers for polyvinylchloride and similar plastics. They may be incorporated e.g. on a crew extruder as is usual with incorporating additives in plastics and may be used in amounts of from 5 to 50% by weight, preferably 10 to 20% by weight. These additives exert the same plasticizing effect as normally used phthalic acid esters. Their main advantage is in the fact that the substituent on the aromatic nucleus reduces their migration so that plastics which contain the products of this invention as plasticizers especially polyvinylchloride will not give off these additives in the course of time.
• the instant compounds are also intermediates for producing coating materials, such as lacquers and films, resistant to high temperatures, as disclosed and claimed in copending US. application Ser. No. 745,401, filed July 17, 1968, now Pat. No. 3,503,928.
• the dimethyl ester of 4-amino-4-phenoxyphthalic acid is saponified in a methanolic solution of potassium hydroxide under refiux in an atomsphere of nitrogen.
• the hydrochloride of 4'-amino-4-phenoxyphthalic acid is prepared by introducing the methanolic solution dropwise into a mixture of 50% water and 50% concentrated hydrochloric acid, and it is then recrystallised from water. 5 g. of the hydrochloride of 4'-amino-4-phenoxyphthalic acid are suspended in purified thionyl chloride at room temperature and stirred until no further evolution of gas can be observed (6 to 8 hours).
• the thionyl chloride is re moved by evaporation and the chloride of 4'ammonium- 4-phenoxy-phthalic acid anhydride remaining behind is dissolved in 25 ml. of anhydrous pyridine without further purification and stirred for 4 hours at 25 C.
• a viscous solution is obtained which is divided into two halves. One half is poured on a glass plate and heated under nitrogen, first at 150 C. for one hour and then at 300 C. for 30 minutes. The resulting film can withstand temperatures above 400 C. without visible damage.
• the second half of the solution is introduced dropwise into dilute acetic acid and the resulting precipitate of polyamidocarboxylic acid is filtered off, washed with methanol and water and dried under vacuum.
• the product can be stored for some time in this form.
• 1 g. of the polyamidocarboxylic acid is dissolved in 4 ml. of dimethyl formamide and converted as described above into a polyimide film which has the same properties.
• Heat distortion temperature 560 C.
• Example 1 was repeated using a solution of 4.0 g. (0.1 mol) of sodium hydroxide in 10 ml. of water in place of the sodium methylate. The water was distilled off azeotropically with toluene, and the solution of p-chlorom'trobenzene was then added. Yield: 25 g.
• R* is alkyl of 1 to 6 carbon atoms, phenyl or naphthyl.

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

Applications Claiming Priority (1)

Publications (1)

Family

ID=7105965

Family Applications (1)

Country Status (7)

Cited By (3)

• 1967
  • 1967-07-26 DE DE19671643333 patent/DE1643333A1/de active Pending
• 1968
  • 1968-04-18 CH CH575068A patent/CH499483A/de not_active IP Right Cessation
  • 1968-06-13 GB GB28091/68A patent/GB1202166A/en not_active Expired
  • 1968-07-18 US US745707A patent/US3686266A/en not_active Expired - Lifetime
  • 1968-07-25 NL NL6810545A patent/NL6810545A/xx unknown
  • 1968-07-25 BE BE718564D patent/BE718564A/xx unknown
  • 1968-07-26 FR FR1573736D patent/FR1573736A/fr not_active Expired

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