US2790824A - Oxidation of hydroxyl-containing aliphatic compounds - Google Patents

Oxidation of hydroxyl-containing aliphatic compounds Download PDF

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Publication number
US2790824A
US2790824A US371711A US37171153A US2790824A US 2790824 A US2790824 A US 2790824A US 371711 A US371711 A US 371711A US 37171153 A US37171153 A US 37171153A US 2790824 A US2790824 A US 2790824A
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reaction
acid
cleavage
lead
group
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US371711A
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Inventor
Philip C Daidone
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Baker Castor Oil Co
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Baker Castor Oil Co
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Priority to US371711A priority Critical patent/US2790824A/en
Priority to GB13706/54A priority patent/GB759416A/en
Priority to NL187897D priority patent/NL187897B/xx
Priority to NL187897A priority patent/NL88892C/xx
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
    • C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
    • C11C3/006—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by oxidation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C07C45/29—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of hydroxy groups
    • C07C45/296—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of hydroxy groups with lead derivatives
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
    • C07C45/673—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by change of size of the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/09—Preparation of carboxylic acids or their salts, halides or anhydrides from carboxylic acid esters or lactones
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
    • C07C51/373—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by introduction of functional groups containing oxygen only in doubly bound form
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C59/00—Compounds having carboxyl groups bound to acyclic carbon atoms and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
    • C07C59/185—Saturated compounds having only one carboxyl group and containing keto groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C59/00—Compounds having carboxyl groups bound to acyclic carbon atoms and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
    • C07C59/40—Unsaturated compounds
    • C07C59/42—Unsaturated compounds containing hydroxy or O-metal groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/035—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with saturated hydrocarbons

Definitions

  • dracrylic acid, citric acid and the alkali metal salts thereof malic acid, citramalic acid, agaracinic acid, norcaperatic acid, beta-hydroxybutyr-ic acid, beta hydroxyvaleric acid, beta-hydroxyisovaleric acid, beta-acetylethyl alcohol, 2,5-hexanedion-3-ol, diacetone alcohol, methylacetonyl carbinol, and aldol condensation products as exemplified by acetaldol and heptaldol, as well as ricinoeyl derivatives, such as methyl ricinoleate, butyl ricinoleate, castor oil, ricinoleic acid, ricinolleyl alcohol, ricinoleic acid salts, and ricinoleic amides.
  • the tetravalent lead compounds suitable for use in effecting the oxidative cleavage reactions, are tetravalent lead salts of aliphatic carboxylic acids having from 2 to 6 carbon atoms per molecule, such as acetic acid, propionic acid, pivalic acid, and caproic acid. Tetravalent lead compounds which yield salts with these acids are also satisfactory for use in the process of this invention. Such compounds include red lead and lead dioxide. It is deatcnt phase separation,
  • Thecleavage reaction is carried out in the presence of a suitable solvent, such as one of the aforesaid aliphatic carboxylicacids having from 2 to 6 carbon atoms per molecule.
  • a suitable solvent such as one of the aforesaid aliphatic carboxylicacids having from 2 to 6 carbon atoms per molecule.
  • This acid should be present in suificient amount to dissolve the aliphatic compound being oxidized.
  • tetravalent lead salt is being formed in situ, sufficient additional aliphatic acid should be present to react with the lead compound charged to the reactor.
  • suitable reaction media include aromatic hydrocarbons, nitro-aromatic hydrocarbons, and chlorinated aliphatic hydrocarbon, typical examples of such solvents being benzene, nitro-benzene, chloroform, carbon tetrachloride, and di-chloroethylene.
  • the cleavage reaction proceeds at temperatures ranging from about 10to-.about 200 C.
  • the maximum reaction temperature will be governed by the boiling point ofthe solvent, as it is preferable to conduct the reaction below such boiling point.
  • the preferred reaction temperature is in the range from about 35 C. to about 45 C. Since the cleavage reaction is exothermic, cooling of thereaction mixture is required in order to maintain the preferred reaction temperature. A measure of the completion of the reaction is given by the point beyond which cooling-ofthereaction mixture is not required to maintain the temperaturein the preferred range.
  • the recovery of the reaction products is preferably effected, in the case of ricinoleyl compounds,'by mixing the reaction mixture with a large volume of water to cause a separating the upper phase, washing that phase free from aliphatic acid and lead compounds, and distilling the washed phase to. recover a distillate and an acyloxy aliphatic compound as'a residue.
  • Steam distillation orspargingwith carbon dioxide are desirable methods of effecting the indicated distillation step.
  • the distillate and residue may be dried by methods known to the art, such as by drying them over anhydrous sodium sulfate.
  • the purity of the dried fractions can be improved by subjecting them to vacuum distillation. Modifications of this technique can be used in recovering the cleavage products formed from non-ricinoleyl starting materials.
  • the process of this invention appears to involve a cleavage reaction, the cleavage taking place at the bond joining the carbon atoms to which the R and R groups are attached, as per the above general formula for the grouping which is characteristic of the starting materials for this invention.
  • the cleavage product containing the R group is an aldehyde when R is hydrogen, and otherwise is a keto derivative.
  • the other cleavage product, to which the R groupis attached, is characterizedby having an acyloxy group (from the tetravalent lead compound) attached to the carbon atom bearing the R group.
  • the process of this invention can serve as a means of preparing, either directly or through modification of the cleavage reaction products, a series of aldehydes, ketones, saturated and unsaturated hydroxy acids, diols, dibasic acids, and their corresponding acyloxy and alkyl and aryl esters.
  • cleavage could be eflected in the case of compounds containing adjacent hydroxyl groups. It has also been known that compounds such as lead tetraacetate will acetoxylate nonhydroxy compounds containing active methylene groups, but, in the case of such compounds, no cleavage occurs. According to the present invention, it has been found that cleavage occurs in compounds containing one hydroxyl group, which is attached to a carbon atom which is adjacent to a carbon atom bearing an active hydrogen atom; additionalhydroxy groups may be present, provided that no hydroxyl group is attached to the carbon atom bearing the active hydrogen atom. If there is no hydroxyl group in the molecule, acyloxylation is the only reaction which occurs.
  • Example 1 Preparati0n of lead tetraacetate 5530 parts by weight of glacial acetic acid and 3920 parts by weight of acetic anhydride were added to a glass flask which was partially submerged in a steam bath.
  • Example 2.0xidation of sodium citrate A solution of sodium citrate in acetic acid was prepared. Lead tetraacetate cake was added in portions to this solution. stoichiometric excess, so as to ensure the complete reaction of the lead tetraacetate. Upon the addition of the lead tetraacetate, an exothermic reaction took place with the formation of a yellow precipitate. The latter was separated by filtration, washed with water to remove unreacted sodium citrate and acetic acid, and dried. The
  • product is a mixture of the salts of oxaloacetic acid and acetoxyglycolic acid.
  • Example 3.-0xidation. of diacetone alcohol A solution of diacetone alcohol in acetic acid was prepared, and to it was added lead tetraacetate cake, the diacetone alcohol being in slight stoichiometric excess. The system was heated to about 85 C., whereupon vigorous reaction took place. Water washing of the reaction product removed one of the products, acetone. The other product, insoluble in water, was acetoxyacetol, and this product wasdried over anhydrous sodium sulfate. This product was obtained in good yield. 7
  • Example 4.- -Oxia'ation of heptaldol The reaction of heptaldol with lead tetraacctatein slight stoichiometric excess in benzene solution was carried out at 35-45 C. The reaction was completed in hours, the reaction mixture being vigorously stirred during this period. The products of the cleavage reaction, heptaldehyde and alpha-acetoxy-heptaldehyde, were isolated and recovered in good yields.
  • Example 5 0xidation of methyl ricinoleate Approximately 5500 parts by weight of lead tetraacetate, in the form of the moist cake, together with 2030 parts by weight of methyl ricinoleate and 2265 parts by weight of glacial acetic acid, were placed in a glass flask which was partially submerged in a cooling bath. The flask contents were vigorously mixed for 15 hours, the temperature thereof not being allowed to go higher than 40 C. The unreacted lead tetraacetate was then separated by filtration. The resulting filtrate was mixed with 4000 parts by weight of Water to cause a phase separation. The top phase was separated, washed free of acetic acid and lead acetate. and the washings were discarded.
  • the sodium citrate was used in slight (543 parts by weight) was added in increments.
  • the washed phase was then subjected to steam distillation.
  • the heptaldehyde layer was separated from the condensate, and was dried over anhydrous sodium sulfate; the yield of the crude heptaldehyde was 420 parts by weight.
  • the top layer of the. distillation residue was separated and dried over sodium sulfate; this product, principally methyl 11-acetoxy-9-undecenoate, was obtained in a yield of 1745 parts by weight.
  • the heptaldehyde was identified by redistillation, and preparation of the oxime from a portion of the purified material; the melting point of the oxime corresponded to that for the oxime of heptaldehyde, and was unchanged when the experimental oxime was mixed with known heptaldoxime.
  • the indicated methyl ester product, on vacuum distillation, was found to have a boiling point of 80-83 C. at 0.5 mm. and a saponification value of 421.7 (theoretical value: 438). Saponification of the methyl ester, followed by acidification, yielded 11-hydroxy-9- undecenoic acid, which was found to have the following analytical constants:
  • Azelaic acid was obtained from the methyl ester of acetoxy undecenoic acid by oxidation with potassium permangamate. This showed that the double bond in the undecenoic acid ester was in the 9-10 position.
  • Example 7.-Oxidati0n of methyl ricz'noleate Example 5 was repeated, using .caproic acid as the reaction medium and lead tetracaproate as the cleavage reagent The reaction temperature was maintained at about C. 1 The heptaldehydeformed in this reaction was recovered as indicated in Example 5; the other prod uct, methyl- 1l-capro-oxy-9-undecenoate, was also recovered in good yields, the recovered product having a saponification value of 357.2 (theoretical .value: 368.5).
  • Example 9 --xidation of castor oil 2030 parts by weight of No. 1 castor oil were reacted With a slight stoichiometric excess of lead tetraacetate cake in 2265 parts by weight of glacial acetic acid, according to the method used in Example 5. The heptaldehyde was separated from the washed product by carbon dioxide sparging. The acetoxy product, glyceryl tri-(llacetoxy-9-undecenoate), was obtained in good yield (1796 parts by weight) and had an iodine value of 90.2 (theoretical value: 99.5).
  • Example 10 -Oxidation of butyl ester of castor oil fatty acids 2380 parts by weight of the butyl ester of castor oil fatty acids were reacted with a slight stoichiometric excess of lead tetraacetate according to the method of Example 5. The heptaldehyde was removed from the washed product by carbon dioxide sparging. The acetoxy product, butyl 11-acetoxy-9-undecenoate, was vacuum distilled; the iodine value of the purified material was 83.0 (theoretical value: 82.2).
  • Example 11.0xidati0n of castor oil fatty acids Example was repeated, substituting castor oil fatty acids for the methyl ricinoleate.
  • Example I 2.Oxidation of m thyl ricinoleate Example 5 was repeated, using dichloroethylene as the reaction medium instead of glacial acetic acid. The reaction :and product were substantially identical to those reported under Example 5.
  • said tetravalent lead compound is a salt of an alkyl carboxylic acid having from 2 to 6 carbon atoms per molecule.
  • tetravalent lead compound is one which yields salts of alkyl carboxylic acids having from 2 to 6 carbon atoms per molecule on in situ reaction with said acids.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US371711A 1953-07-31 1953-07-31 Oxidation of hydroxyl-containing aliphatic compounds Expired - Lifetime US2790824A (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
US371711A US2790824A (en) 1953-07-31 1953-07-31 Oxidation of hydroxyl-containing aliphatic compounds
GB13706/54A GB759416A (en) 1953-07-31 1954-05-11 Improvements relating to cleavage products of aliphatic compounds
NL187897D NL187897B (en:Method) 1953-07-31 1954-05-26
NL187897A NL88892C (en:Method) 1953-07-31 1954-05-26

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US371711A US2790824A (en) 1953-07-31 1953-07-31 Oxidation of hydroxyl-containing aliphatic compounds

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GB (1) GB759416A (en:Method)
NL (2) NL187897B (en:Method)

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GB759416A (en) 1956-10-17
NL88892C (en:Method) 1958-07-16
NL187897B (en:Method) 1958-03-15

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