Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
  • C07C69/76—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring
  • C07C69/80—Phthalic acid esters
  • C07C69/82—Terephthalic acid esters
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
  • C07C31/34—Halogenated alcohols
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C67/00—Preparation of carboxylic acid esters
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C67/00—Preparation of carboxylic acid esters
  • C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C67/00—Preparation of carboxylic acid esters
  • C07C67/24—Preparation of carboxylic acid esters by reacting carboxylic acids or derivatives thereof with a carbon-to-oxygen ether bond, e.g. acetal, tetrahydrofuran
  • C07C67/26—Preparation of carboxylic acid esters by reacting carboxylic acids or derivatives thereof with a carbon-to-oxygen ether bond, e.g. acetal, tetrahydrofuran with an oxirane ring
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
  • C07C69/62—Halogen-containing esters
  • C07C69/63—Halogen-containing esters of saturated acids
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
  • C07C69/76—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
  • C07C69/76—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring
  • C07C69/78—Benzoic acid esters

Definitions

• the present invention relates to ethylene glycol monoesters. More particularly, it relates to a-monochlorohydrin monoesters of carboxylic acids. Even more particularly, the invention relates to an improved process for the preparation of :x-monochlorohydrin monoesters of saturated aliphatic and aromatic carboxylic acids.
• ethylene glycol monoesters may be prepared from saturated carboxylic acids, either alone or in mixture with each other, and ethylene oxide. Stoichiometric or excess quantities of ethylene oxide may be used. According to such known processes, the reaction is carried out in the absence of catalysts at temperatures of from 25 to 200 C., preferably between 80 and 160 C., and in the presence of a mixture of water and neutral inorganic alkali metal salts, such as chlorides and/ or nitrates and/ or sulfates. Amounts of up to 40% by weight, based on the amount of saturated carboxylic acid employed, of the inorganic alkali metal salts are used in these processes.
• One of the objects of the present invention is to provide an improved process for the preparation of ethylene glycol monoesters, specifically a-monochlorohydrin monoesters of saturated aliphatic and aromatic carboxylic acids, which overcomes the disadvantages and deficiencies of the prior art processes.
• Another object of the present invention is to provide a process for the preparation of a-monocblorohydrin monoesters of saturated aliphatic and aromatic carboxylic acids which may be carried out in an efficacious and convenient manner.
• a further object of the invention is to provide a process that yields cz-InOnOChlOIOhYdl'iIl monoesters of saturated aliphatic and aromatic canboxylic acids in high purity and good yield.
• a still further object of the invention is to provide a process for the preparation of a-mon'ochlorohydrin monoesters of saturated aliphatic and aromatic cauboxylic acids which may be carried out easily and simply.
• a-monochlorohydrin monoesters of saturated aliphatic and aromatic carboxylic acids may be produced more etlicaciously when utilizing the prior art method of operation described above by reacting such carboxylic acids with epichlorohydrin instead of with ethylene oxide.
• Used as saturated aliphatic or aromatic monoand polycarboxylic acids in the method of the present invention may be, for example, aliphatic carboxylic acids containing 1 to 20.carbon atoms, benzene carboxylic acids such as the benzenetricarboxylic and benzenetetracarboxylic acids and the substitution products thereof, phthalic acids, naphthalic acid, and other acids equivalent to those mentioned herein for the above-defined specified purpose.
• the neutral inorganic alkali metal salts to be used herein are preferably potassium chloride, potassium sulfate, and potassium nitrate.
• alkali metal salts should have a purity of at least the degree known as pure and should be free of by-products which exert catalytic side effects on epichlorohydrin, on the intermediate products or on the end products of the present invention. Condensation and saponification are examples of such undesirable catalytic side effects.
• the corresponding alkaline earth metal salts may be employed, if desired, as long as they are watersoluble and do not yield any difiicultly water-soluble salts during the reaction with the saturated carboxylic acids.
• reaction with epichlorohydrin in accordance with the present invention proceeds generally somewhat more slowly than the prior art reactions with ethylene oxide under comparable conditions. Due to the high boiling point of epichlorohydrin, however, the reaction velocity may be favorably increased by Working at slightly higher temperatures.
• a modification of the process of this invention involves carrying out the reaction by using a molar deficiency of epichlorohydrin and distilling, filtering off or Washing out the excess acid from the end product.
• the products produced according to the process of the present invention are valuable intermediate products for the preparation of plasticizers, resins, and lacquers, generally without any further specific purification thereof.
• the end products may be distilled or recrystallized. Upon further reaction thereof, derivatives of glycerol are obtained.
• Example I A mixture of G. n-Caprylic acid 72 Distilled water 200 Potassium chloride 6 Epichlorohydrin 60 was combined at room temperature in a glass stirring vessel equipped with a reflux cooler. The mixture was heated to 60 C. within one hour While it was vigorously stirred. A sample of the uniformly stirred mixture yielded initially an acid number of 83. After 8 hours, the acid number of the mixture was 17 and after a total of 15 hours, it was 3.5. The monoester precipitated, while standing, as an oily under-layer which was mechani cally separated, neutralized while stirring with a few drops of an n/2 (0.5 normal) solution of caustic potash (potassium hydroxide) and finally washed. The product thus obtained was distilled under vacuum until it was free from water and epichlorohydrin. As final product, there was obtained 109 grams of crude monoester, which represented a 91.3% yield. The product had the following characterizing numbers:
• the crude product had a weight of 174 grams, representing 99% of the theoretical yield. It had the following characterizing numbers:
• the ester can be distilled easily. It passes over at between 122 to 124 C. and at 14 mm. Hg pressure as a viscous water-clear liquid having a faint odor. This odor is not a butyric acid odor. After distillation, the following characterizing numbers were found for the product:
• the product consisted of an oily and an aqueous phase.
• the oily phase was mechanically separated and distilled.
• 96 grams of o-chlorobenzoic acid-a-monochlorohydrin monoester 77% of the theoretical yield, was obtained as the main fraction within a boiling range of between 151 and l52.5 C. at 0.7 mm. Hg pressure.
• the yield may be further increased by returning the preliminary run of the distillation and the residue to the reaction mixture.
• Another portion contains the aqueous phase which also can be returned thereto.
• the following characterizing numbers were found for the main fraction:
• Example VII A reaction batch of Benzoic acid, Sublimated 122 Water, distilled 300 Potassium sulfate, crystallized 8 Epichlorohydrin, commercial 110 was combined at room temperature in a stirring vessel equipped with a reflux cooler and heated to 90 C. within 15 minutes. The acid number was 22 after 7 hours. While stirring, neutralization was effected with an n/2 solution of caustic potash.
• the oily layer was mechanical- 1y separated, washed twice with a little Water, rendered Waterand epichlorohydrin-free under vacuum, and filtered over active carbon.
• Example VIII A mixture of G. Capric acid, about a 90% solution 86 Water, distilled 250 Potassium chloride, chemically pure Epichlorohydrin, commercial 55 was treated as indicated in Example VII. After a total reaction time of 1.5 hours, the acid number was 4.8. After further treatment as described in Example VH, 124 grams of monoester were obtained which had the following characterizing numbers:
• Example IX An initial mix of G. Terephthalic acid monomethyl ester 90 Water, distilled 350 Potassium chloride, chemically pure 10 Epichlorohydrin, commercial 60 was combined at room temperature in a cylindrical vessel equipped With a stirrer and a reflux cooler and heated to 90 C. within 30 minutes. After a total time of 3 /2 hours, the reaction mixture was stirred in the cold and neutralized, while intensively stirring, with a 20% solution of aqueous caustic potash, using phenolphthalein as indicator therefor. Suction was effected thereafter, washing with water carried out, and the solid constituents dried. Obtained were 94 grams, representing 69% of the theoretical yield of terephthalic acid monomethyl-amonochlorohydrin monoester having the following characterizing numbers:
• the yield is dependent upon the intensity of stirring because the reaction product forms flocks and inclusions during the reaction.
• a process for the preparation of tit-monochlorohydrin monoesters of carboxylic acids which comprises reacting a carboxylic acid selected from the group consisting of saturated aliphatic and aromatic carboxylic acids with epichlorohydrin in the presence of water and an inorganic compound selected from the group consisting of neutral inorganic alkali metal salts and neutral Watersoluble inorganic alkaline earth metal salts.
• a process for the preparation of zit-monochlorohydrin monoesters of carboxylic acids which comprises reacting a carboxylic acid selected from the group consisting of saturated aliphatic and aromatic carboxylic acids with epichlorohydrin at a temperature of between 25 and 200 C. in the presence of water and up to 40% by weight, based on the Weight of carboxylic acid employed, of an inorganic compound selected from the group consisting of neutral inorganic alkali metal salts and neutral Watersoluble inorganic alkaline earth metal salts, and separating the resulting monoester product from the reaction mixture.

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• 1963
  • 1963-10-22 DE DEC31208A patent/DE1198342B/de active Pending
• 1964
  • 1964-10-19 FR FR34849A patent/FR1412108A/fr not_active Expired
  • 1964-10-20 US US405265A patent/US3321500A/en not_active Expired - Lifetime

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