US2811538A - Preparation of organic acids by the - Google Patents
Preparation of organic acids by the Download PDFInfo
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- US2811538A US2811538A US2811538DA US2811538A US 2811538 A US2811538 A US 2811538A US 2811538D A US2811538D A US 2811538DA US 2811538 A US2811538 A US 2811538A
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- United States
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- acids
- acid
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- parts
- saturated aliphatic
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- 150000007524 organic acids Chemical class 0.000 title description 14
- 235000005985 organic acids Nutrition 0.000 title description 14
- 238000002360 preparation method Methods 0.000 title description 12
- 239000002253 acid Substances 0.000 claims description 156
- 150000007513 acids Chemical class 0.000 claims description 94
- -1 HYDROXYL GROUPS Chemical group 0.000 claims description 56
- 239000003518 caustics Substances 0.000 claims description 46
- 150000001991 dicarboxylic acids Chemical class 0.000 claims description 18
- 238000004519 manufacturing process Methods 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 8
- 150000002763 monocarboxylic acids Chemical class 0.000 claims description 8
- 150000001298 alcohols Chemical class 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 2
- 239000000203 mixture Substances 0.000 description 52
- 150000002148 esters Chemical class 0.000 description 46
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 36
- 238000000034 method Methods 0.000 description 34
- 230000004927 fusion Effects 0.000 description 32
- RTZKZFJDLAIYFH-UHFFFAOYSA-N diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 24
- 125000004432 carbon atoms Chemical group C* 0.000 description 22
- 125000001931 aliphatic group Chemical group 0.000 description 20
- 230000001264 neutralization Effects 0.000 description 20
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Chemical class [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 20
- 150000003839 salts Chemical class 0.000 description 20
- 239000011780 sodium chloride Substances 0.000 description 20
- 239000007864 aqueous solution Substances 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- 239000003513 alkali Substances 0.000 description 14
- 239000002480 mineral oil Substances 0.000 description 14
- 235000010446 mineral oil Nutrition 0.000 description 14
- 235000011121 sodium hydroxide Nutrition 0.000 description 14
- 239000008346 aqueous phase Substances 0.000 description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 10
- 239000003960 organic solvent Substances 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 239000011369 resultant mixture Substances 0.000 description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 125000004093 cyano group Chemical group *C#N 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000003921 oil Substances 0.000 description 8
- 235000019198 oils Nutrition 0.000 description 8
- 235000011118 potassium hydroxide Nutrition 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 239000003760 tallow Substances 0.000 description 8
- SSHYKTQAIFRQRJ-UHFFFAOYSA-N C(#N)C(C(=O)O)(CCCCCCCCCCCCCCCC)O Chemical compound C(#N)C(C(=O)O)(CCCCCCCCCCCCCCCC)O SSHYKTQAIFRQRJ-UHFFFAOYSA-N 0.000 description 6
- TVMXDCGIABBOFY-UHFFFAOYSA-N Octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 6
- 125000005907 alkyl ester group Chemical group 0.000 description 6
- 238000010504 bond cleavage reaction Methods 0.000 description 6
- 238000004821 distillation Methods 0.000 description 6
- 239000003925 fat Substances 0.000 description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000011541 reaction mixture Substances 0.000 description 6
- UKMSUNONTOPOIO-UHFFFAOYSA-N Behenic acid Natural products CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 4
- MTHSVFCYNBDYFN-UHFFFAOYSA-N Diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N HCl Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N Oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N Sebacic acid Natural products OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 4
- QIQXTHQIDYTFRH-UHFFFAOYSA-N Stearic acid Chemical class CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 4
- 238000007792 addition Methods 0.000 description 4
- 150000001536 azelaic acids Chemical class 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 238000005755 formation reaction Methods 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 4
- 150000004702 methyl esters Chemical class 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 239000011707 mineral Substances 0.000 description 4
- 235000010755 mineral Nutrition 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 150000003330 sebacic acids Chemical class 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000012258 stirred mixture Substances 0.000 description 4
- WXZMFSXDPGVJKK-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- LTYRAPJYLUPLCI-UHFFFAOYSA-N 2-hydroxyacetonitrile Chemical class OCC#N LTYRAPJYLUPLCI-UHFFFAOYSA-N 0.000 description 2
- 235000017060 Arachis glabrata Nutrition 0.000 description 2
- 240000005781 Arachis hypogaea Species 0.000 description 2
- 235000010777 Arachis hypogaea Nutrition 0.000 description 2
- 235000018262 Arachis monticola Nutrition 0.000 description 2
- 235000021357 Behenic acid Nutrition 0.000 description 2
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Natural products OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 240000007842 Glycine max Species 0.000 description 2
- 235000010469 Glycine max Nutrition 0.000 description 2
- 240000006669 Helianthus annuus Species 0.000 description 2
- 235000003222 Helianthus annuus Nutrition 0.000 description 2
- 240000006240 Linum usitatissimum Species 0.000 description 2
- 235000004431 Linum usitatissimum Nutrition 0.000 description 2
- 239000005642 Oleic acid Substances 0.000 description 2
- 240000001090 Papaver somniferum Species 0.000 description 2
- 235000008753 Papaver somniferum Nutrition 0.000 description 2
- 235000004347 Perilla Nutrition 0.000 description 2
- 240000003877 Perilla frutescens Species 0.000 description 2
- 235000004348 Perilla frutescens Nutrition 0.000 description 2
- 235000019484 Rapeseed oil Nutrition 0.000 description 2
- 241001125046 Sardina pilchardus Species 0.000 description 2
- 240000003670 Sesamum indicum Species 0.000 description 2
- 235000003434 Sesamum indicum Nutrition 0.000 description 2
- MNWBNISUBARLIT-UHFFFAOYSA-N Sodium cyanide Chemical compound [Na+].N#[C-] MNWBNISUBARLIT-UHFFFAOYSA-N 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- 240000008042 Zea mays Species 0.000 description 2
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 235000019445 benzyl alcohol Nutrition 0.000 description 2
- 150000003938 benzyl alcohols Chemical class 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 235000005822 corn Nutrition 0.000 description 2
- 235000005824 corn Nutrition 0.000 description 2
- 235000012343 cottonseed oil Nutrition 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 235000004426 flaxseed Nutrition 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 239000004519 grease Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 235000014571 nuts Nutrition 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N palmitic acid group Chemical group C(CCCCCCCCCCCCCCC)(=O)O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- 235000020232 peanut Nutrition 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 150000007519 polyprotic acids Polymers 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 2
- 235000019512 sardine Nutrition 0.000 description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/097—Preparation of carboxylic acids or their salts, halides or anhydrides from or via nitro-substituted organic compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/02—Preparation of carboxylic acids or their salts, halides or anhydrides from salts of carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
-
- 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
- C07C59/01—Saturated compounds having only one carboxyl group and containing hydroxy or O-metal groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
- C07C69/67—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of saturated acids
- C07C69/675—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of saturated acids of saturated hydroxy-carboxylic acids
Definitions
- This invention relates to the preparation of -organic acids. It relates to the preparation'of'dicarboxylic acids and'monocarboxylic acids. l
- the object of this invention is to provide an economical and commerciallypracticable method of manufacturing monobasic and dibasic organic acids ⁇
- This and other "objects are accomplished by the process of this invention which comprises reacting molten caustic alkali at a temperaturefrom abOut'ZOO C. to about 400 C. with a saturated aliphatic acid which contains l6 to 22 carbon atoms, or withan ester of such an acid, said acid also containing vicinal cyano-hydroxy substituents.
- the invention comprises subjectingtocaustic fusion an ,acid, or an ester thereof, which acid contains 16jto 22 carbon atoms and also contains in the acid chain a group of thestructure, v
- the cyano-hydroxy acids and esters which are emif ployed in this process are the subject of another application for Letters Patent, Serial No. 518,983, filed June 29, 1955. They are prepared by reacting an epoxidized aliphatic acid containing 16 to 22 carbon atoms, or an ester thereof, with Theiacids which are-subjected to caustic fusion by the process of this invention are, therefore, the cyano-hydroxy derivatives .,of palmitic, margaric, stearic, nondecoic, ara- "chi dic,. eicosic' and behenic acids, of which substituted stearic acid is the preferred species.
- the instant invention also embraces the caustic fusion of the esters of the above-described cyano-hydroxy acids as well asof the acids, per se.
- the operable esters are those of the acids and monohydric or polyhydric alcohols which are typified by the following: methyl, ethyl, iso- 'propy1, n-butyl, sec-butyl, tert-butyl, tert-amyl, n-octyl, Z-ethylhexyl, lauryl, octadecyl, cyclohexyl and benzyl alcohols; ethylene glycol, 1,2-propylene glycol, 2-ethylhexandiol-l,3, butandiol-1,3,-butandiol-l,4, dodecandiol- 1,l2; diethylene glycol; glycerol; pentaerythritol; and the isomers and homologues of the
- cyano-hydroxy glyceridicesters namely the substitutednaturaloilsand fats, areincluded in this last category and they are typified by. the following cyano-hydroxylated materials: tallow and soybean, corn, cottonseed, safilower, sunflower, sesame, poppy'seed,,wal-I nut, peanut, linseed, perilla and sardine oils.
- the cyano-hydroxy derivative is added to the liquid caustic reactant at a temperature from about 200 C. to about 400 C. It is much preferred to employ temperatures from about; 310 C. to about 340 C.
- the caustic and the ester or acid can be mixed and heated together; or the caustic can be added to the heated acid or ester.
- the addition of water aids in the melting or fusionof the caustic, especially at the lower operating temperatures.
- ordinary commercial grades of sodium and potassium hydroxides contain some'water which aids in the fusion of these materials.
- the important consideration is that the reaction mixture of caustic and the acid or ester be fluid at the temperature of reaction. Obviously the reaction can be carried out at superatmospheric temperatures as well as at atmospheric pressure. I p
- the oxides or hydroxides of lithium and of the alkaline earthmetals can be used, it is much preferred to employ sodium hydroxide or potassium hydroxide or mixtures of the two for the sake of economy and efiiciency. It is also recommended that an inert liquid such as mineral oil or white oil be present during the caustic fusion reaction. Such a material, although not essential, serves as a flux and greatly facilitates the stirring and mixing of the reactants. I V After the caustic fusion the scission products are sep* arated. By the preferred procedure, thecooled reaction mixture, which is usually a soap-like mass is treatedwith water in order to dissolve the salts or soaps of the organic acids which have formed.
- an inert liquid such as mineral oil or white oil
- an organic solvent such as mineral oil
- a low-boiling organic liquid such as diethyl ether or petroleum ether which is later separated from the high-boiling solvent by distillation.
- the aqueous solution is then acidified with a strong mineral acid, such as hydrochloric acid or sulfuric acid; and the free organic acids which are thus formed are next removed by extrac tion with an organic solvent, such as diethyl ether.
- the organic solvent is stripped off and a mixture of monobasic and polybasic acids is thereby obtained.
- the mixture is dissolved in a dilute solution of a caustic alkali, preferably sodium hydroxide, in an amount sufficient to convert the organic acids to soluble salts.
- a caustic alkali preferably sodium hydroxide
- the resultant aqueous solution of salts is mixed with an organic solvent, preferably an inert hydrocarbon such as octane, and the mixture is again acidified with a strong mineral acid to a pH Which is no lower thanabout 5.5.
- an organic solvent preferably an inert hydrocarbon such as octane
- the aqueous solution is then further acidified to a pH of about 1.5 to 2 and is also preferably cooled to about 5 C.
- the dibasic acids which then precipitate are filtered off and are washed with water and later dried.
- This procedure for separating monobasic and dibasic acids isreferred to herein as ?the pH method.”
- a mixture of all of the salts resulting from a caustic fusion can, itself, be treateddirectly by thepH method of acidulation as a simpler and faster methodof separating and isolating the resultant mixture of monobasic acids on the onehand and the mixture of dibasicacids on theother.
- this asngc'ssalternative eliminates a precipitation step and the redissolving step.
- Example 1 A-mixture of 56'parts'of potassium hydroxide, 40 parts of sodium hydroxide and 120 parts of mineral oil was placed in a reactorequipped with an attachable cover, thermometer, stirrer, and an inlet tube for liquids.
- the stirred mixture was-heated-to320 and was held at 320 to 325 C. while to it was added slowly and; uniformly over a period of approximately one hour 68 parts ofa mixture 9,10 and 10,9-cyanohydroxystearic acid. (The latter had been made by the reaction of sodium cyanide and epoxystearic acid in methanol.)
- the stirred reaction mixture was held at 320 to 325 C. for an additional hour. The mass was allowed to cool and was then added to 800 parts of water.
- the mineral oil was separated and the aqueous phase was extracted with diethyl ether to remove all of the mineral oil.
- the aqueous phase was then acidified to a pH of 1.5 and the precipitated mixture of acids was extracted by means of diethyl ether.
- the separated ether solution was evaporated and a yield of 67 parts of a mixture of acids having a neutral equivalent of 126 was obtained.
- a neutral equivalent obtained by titrating a known quantity of an acid or mixture of acids with standard alkali is a measure of the average molecular weight of the acid for each mole of carboxyl group in the acid or mixture of acids.
- the monobasic and diabasic acids were then separated as follows: The mixture of acids was dissolved in an aqueous solution of sodium hydroxide. To the resultant solution wasadded 100 parts of octane. This mixture was agitated and heated to 80 C. at which point a 50% aqueous solution of sulfuric acid was slowly added until the-aqueous phase had a pH of 5.9. The organic and aqueous phases were separated. The octane was removed by distillation and a mixture of monobasic acids was obtained as a residue. The aqueous phase was then further acidified to a pH of 1.5 and chilled to 5 C. The precipitated mixture of dibasic acids was filtered off, washed and dried. The product amounted to 2416 parts, had a neutral equivalent of 102 andcontained azelaic and sebacic acids in essentially equimolar amounts.
- Example 2 A stirred mixture of 73 parts of sodium hydroxide and parts of mineral oil was heated to 275 C. and to it was added, over a period of an hour, 93 parts of methyl cyanohydroxy--"rapeseedate (i. e., the methyl ester of the cyanohydroxy acids of rapeseed oil containing 3.4% nitrogen) The mixture was heated at 275 C. for an additional half-hour after which it was treated in themanner described in Example 1. The yield was 87 parts of a mixtureof monobasic and dibasic acids-having a neutral equivalent of 142. The acids were isolated by the pH method described above and a yield of- 19.3 parts of dibasic acids having a neutral equivalent of 108 was obtained.
- Example 4" The same procedure was followed-in the caustic fusion of a glyceridie ester; namely the cyanohydroxy derivative of tallow. Thus, .75 parts of that derivative yielded 755 parts of-a mixture-of acids having a neutral equivalent of 200, of which 13.6parts were dibasic acids having a-neutral equivalent of 101 and including azelaic and sebacic acids.
- the process for preparing saturated aliphatic mono carboxylic and dicarboxylic acids which comprises reacting molten caustic alkali, at a temperature from about 200 C. to about 400 C., with a compound from the class consisting. of (a) saturated aliphatic acids containing 16 to 22 carbon atoms and (b) esters of said acids and saturated aliphatic alcohols containing 1 to 4 hydroxyl groups, said compound also containing in its acid chain a group having the formula OH CN (311 rcthereafter dissolving the resultant mixture of salts in water; and acidifying the resultant aqueous solution to precipitate said monocarboxylic and dicarboxylic acids, and isolating said acids.
- a compound from the class consisting. of (a) saturated aliphatic acids containing 16 to 22 carbon atoms and (b) esters of said acids and saturated aliphatic alcohols containing 1 to 4 hydroxyl groups, said compound also containing in its acid chain a group having the formula
- the process for preparing saturated aliphatic monocarboxylic and dicarboxylic acids which comprises rcacting molten caustic alkali, at a temperature from about 310 C. to about 340 C. with a lower alkyl ester of a saturated aliphatic acid which contains 16 to 22 carbon atoms and which also contains a cyano group and an hydroxyl group on vicinal carbon atoms; thereafter dissolving the resultant mixture of salts in water; and acidifying the resultant aqueous solution to precipitate said saturated aliphatic monocarboxylic and dicarboxylic acids and isolating said acids.
- the process for preparing saturated aliphatic monobasic and dibasic acids which comprises reacting molten caustic alkali, at a temperature from about 200 to about 400 C., with a glyceridic ester of a saturated aliphatic acid which contains 16 to 22 carbon atoms and which also contains a cyano and an hydroxyl group on vicinal carbon atoms; thereafter dissolving the resultant mixture of salts in water; and acidifying the resultant aqueous solution to precipitate said saturated aliphatic monocarboxylic and dicarboxylic acids and isolating said acids.
Description
United States PatentO PREPARATION OF ORGANIC ACIDS BY THE CAUSTIC FUSION OF v.CYANOHYDRIN Edward F. Riener, Haddonfield, N. J., assig nor toRohm &'Haas Company, Philadelphia," Pa.,a corporation ofgDelaware N0 Drawing. Applicationlune 29, 19 55, 1
Serial N0. 518,982
7 Claims. c1.z60, 406
This invention relates to the preparation of -organic acids. It relates to the preparation'of'dicarboxylic acids and'monocarboxylic acids. l
The object of this invention is to provide an economical and commerciallypracticable method of manufacturing monobasic and dibasic organic acids} This and other "objects are accomplished by the process of this invention which comprises reacting molten caustic alkali at a temperaturefrom abOut'ZOO C. to about 400 C. with a saturated aliphatic acid which contains l6 to 22 carbon atoms, or withan ester of such an acid, said acid also containing vicinal cyano-hydroxy substituents.
Thus the invention comprises subjectingtocaustic fusion an ,acid, or an ester thereof, which acid contains 16jto 22 carbon atoms and also contains in the acid chain a group of thestructure, v
(IJN (I)H The cyano-hydroxy. derivatives of a given acid or ester split inlessentiallythe same way, when fused with caustic, toyield mixtures of essentially the same monocarboxylic and dicarboxylic acids. V
The cyano-hydroxy acids and esters which are emif ployed in this process are the subject of another application for Letters Patent, Serial No. 518,983, filed June 29, 1955. They are prepared by reacting an epoxidized aliphatic acid containing 16 to 22 carbon atoms, or an ester thereof, with Theiacids which are-subjected to caustic fusion by the process of this invention are, therefore, the cyano-hydroxy derivatives .,of palmitic, margaric, stearic, nondecoic, ara- "chi dic,. eicosic' and behenic acids, of which substituted stearic acid is the preferred species.
. The instant invention also embraces the caustic fusion of the esters of the above-described cyano-hydroxy acids as well asof the acids, per se. The operable esters are those of the acids and monohydric or polyhydric alcohols which are typified by the following: methyl, ethyl, iso- 'propy1, n-butyl, sec-butyl, tert-butyl, tert-amyl, n-octyl, Z-ethylhexyl, lauryl, octadecyl, cyclohexyl and benzyl alcohols; ethylene glycol, 1,2-propylene glycol, 2-ethylhexandiol-l,3, butandiol-1,3,-butandiol-l,4, dodecandiol- 1,l2; diethylene glycol; glycerol; pentaerythritol; and the isomers and homologues of the above. Since the alcohol portions of the esters do. not contribute anything to the formation of acids and are actually destroyed during the caustic fusion, itis preferredto employ the cheapest and most' re'adily available 'esterso fthe substituted acids.
These are the lower alkyl esters, namely "the methyl, ethyl,
propyl, and butyl esters of the acids and also the natural- 1y occurring esters. The cyano-hydroxy glyceridicesters, namely the substitutednaturaloilsand fats, areincluded in this last category and they are typified by. the following cyano-hydroxylated materials: tallow and soybean, corn, cottonseed, safilower, sunflower, sesame, poppy'seed,,wal-I nut, peanut, linseed, perilla and sardine oils.
In the preferred .embodi ent of the process, of this in: vention, the cyano-hydroxy derivative is added to the liquid caustic reactant at a temperature from about 200 C. to about 400 C. It is much preferred to employ temperatures from about; 310 C. to about 340 C. Alternatively, the caustic and the ester or acid can be mixed and heated together; or the caustic can be added to the heated acid or ester. The addition of water aids in the melting or fusionof the caustic, especially at the lower operating temperatures. As a matter of fact, ordinary commercial grades of sodium and potassium hydroxides contain some'water which aids in the fusion of these materials. The important consideration is that the reaction mixture of caustic and the acid or ester be fluid at the temperature of reaction. Obviously the reaction can be carried out at superatmospheric temperatures as well as at atmospheric pressure. I p
Although the oxides or hydroxides of lithium and of the alkaline earthmetals can be used, it is much preferred to employ sodium hydroxide or potassium hydroxide or mixtures of the two for the sake of economy and efiiciency. It is also recommended that an inert liquid such as mineral oil or white oil be present during the caustic fusion reaction. Such a material, although not essential, serves as a flux and greatly facilitates the stirring and mixing of the reactants. I V After the caustic fusion the scission products are sep* arated. By the preferred procedure, thecooled reaction mixture, which is usually a soap-like mass is treatedwith water in order to dissolve the salts or soaps of the organic acids which have formed. If an organic solvent such as mineral oil has been employed, it is best removed by extraction with a low-boiling organic liquid such as diethyl ether or petroleum ether which is later separated from the high-boiling solvent by distillation. The aqueous solution is then acidified with a strong mineral acid, such as hydrochloric acid or sulfuric acid; and the free organic acids which are thus formed are next removed by extrac tion with an organic solvent, such as diethyl ether. The organic solvent is stripped off and a mixture of monobasic and polybasic acids is thereby obtained. When it is desired to separate the monobasic and dibasic acids, the mixture is dissolved in a dilute solution of a caustic alkali, preferably sodium hydroxide, in an amount sufficient to convert the organic acids to soluble salts. The resultant aqueous solution of salts is mixed with an organic solvent, preferably an inert hydrocarbon such as octane, and the mixture is again acidified with a strong mineral acid to a pH Which is no lower thanabout 5.5. As a result, salts of the monobasic organic acids are converted to the acids per se; and these acids are simultaneously extracted by the organic solvent. After removal of the organic solution, the organic monobasicacids areobtained by distillation of the solvent. The aqueous solution is then further acidified to a pH of about 1.5 to 2 and is also preferably cooled to about 5 C. The dibasic acids which then precipitate are filtered off and are washed with water and later dried. This procedure for separating monobasic and dibasic acidsisreferred to herein as ?the pH method." As an alternative method, a mixture of all of the salts resulting from a caustic fusion can, itself, be treateddirectly by thepH method of acidulation as a simpler and faster methodof separating and isolating the resultant mixture of monobasic acids on the onehand and the mixture of dibasicacids on theother. Obviously this asngc'ssalternative" procedure eliminates a precipitation step and the redissolving step.
The instant process for making monobasic and dibasic acids from cyano-hydroxy acids"and esters is very-'etli ciefitbecause' the number-of scissionproducts isunusually low. Furthermore, .the'processfhas'the advantage of producing 'a'higher'rati'on of dibasic acids to m'onob'asic acids than do 'those processes which utilize other derivatives of acids and l esters.
The following examples; in which all parts are by weight, serve 'to' illustrate theprocess ofthis invention:
Example 1 A-mixture of 56'parts'of potassium hydroxide, 40 parts of sodium hydroxide and 120 parts of mineral oil was placed in a reactorequipped with an attachable cover, thermometer, stirrer, and an inlet tube for liquids. The stirred mixturewas-heated-to320 and was held at 320 to 325 C. while to it was added slowly and; uniformly over a period of approximately one hour 68 parts ofa mixture 9,10 and 10,9-cyanohydroxystearic acid. (The latter had been made by the reaction of sodium cyanide and epoxystearic acid in methanol.) After addition was complete, the stirred reaction mixture was held at 320 to 325 C. for an additional hour. The mass was allowed to cool and was then added to 800 parts of water. The mineral oil was separated and the aqueous phase was extracted with diethyl ether to remove all of the mineral oil. The aqueous phase was then acidified to a pH of 1.5 and the precipitated mixture of acids was extracted by means of diethyl ether. The separated ether solution was evaporated and a yield of 67 parts of a mixture of acids having a neutral equivalent of 126 was obtained. (A neutral equivalent, obtained by titrating a known quantity of an acid or mixture of acids with standard alkali is a measure of the average molecular weight of the acid for each mole of carboxyl group in the acid or mixture of acids.)
The monobasic and diabasic acids were then separated as follows: The mixture of acids was dissolved in an aqueous solution of sodium hydroxide. To the resultant solution wasadded 100 parts of octane. This mixture was agitated and heated to 80 C. at which point a 50% aqueous solution of sulfuric acid was slowly added until the-aqueous phase had a pH of 5.9. The organic and aqueous phases were separated. The octane was removed by distillation and a mixture of monobasic acids was obtained as a residue. The aqueous phase was then further acidified to a pH of 1.5 and chilled to 5 C. The precipitated mixture of dibasic acids was filtered off, washed and dried. The product amounted to 2416 parts, had a neutral equivalent of 102 andcontained azelaic and sebacic acids in essentially equimolar amounts.
This procedure was repeated'many times at varying temperatures as low as 200 C. and using various grades of cyanohydroxystearic acidderived from-varying grades of oleic acid. In all instances the ratio of dibasic acids-to monobasic acids was of the order of at least 1 to 2; and in most instances it approached 1 to 1.
The procedure which has been exemplified above is used inthe caustic fusion of the cyanohydroxy. derivatives of all the aliphatic acids containing 16 to 22 carbon atoms, and also the esters thereof. Obviously, the scission products which are obtained vary depending on the length of the chain of the particular aliphatic acid and also on the positionof the cyano and hydroxyl groups in the acid chains. Furthermore, a mixture of position isomers (e. g., the 9,10- and 10,9-isomers) is invariably obtained in the preparation of the cyanohydroxyacids and esters and this also gives rise to a mixture of scission products. Consequently, in every. case during fusion, a mixture ofthe salts of both monobasicand dibasic acids is inVariableob tained. The monobasic .anddibasicacids are. readily separated by. the so-called pH method described. above. The individual acids can be isolated by chromatography;
althoughinmany industrial applications-for example in the formation resinsthe mixtures of dibasic acids and mixtures of monobasic acids can be used just about as satisfactorily as the individual acids in the mixtures; and consequently the isolation ofthe individual acids is not always necessary.
As' stated above, naturally occurring fats and oils represent-a preferred source of the cyanohydroxy compounds which are converted by the instant process into valuable monobasic and dibasic saturated aliphatic acids. The following examples are typical of the results obtained by the fusion of cyanohydrins obtained from natural fats and oils.
Example 2 A stirred mixture of 73 parts of sodium hydroxide and parts of mineral oil was heated to 275 C. and to it was added, over a period of an hour, 93 parts of methyl cyanohydroxy--"rapeseedate (i. e., the methyl ester of the cyanohydroxy acids of rapeseed oil containing 3.4% nitrogen) The mixture was heated at 275 C. for an additional half-hour after which it was treated in themanner described in Example 1. The yield was 87 parts of a mixtureof monobasic and dibasic acids-having a neutral equivalent of 142. The acids were isolated by the pH method described above and a yield of- 19.3 parts of dibasic acids having a neutral equivalent of 108 was obtained.
The same procedure was employed in the preparation of monobasic and dibasic acids from the caustic fusion of the methyl ester of the cyanohydroxy fatty acids of tallow (containing 1.8% nitrogen). Thus, 69.5 parts of this ester was added dropwise over a period of an hour to a stirred mixture of 56 parts of potassium hydroxide, 40 parts of sodium hydroxide and 120 parts of mineral oil which was held at 255 C. Heating was continued for an additional half-hour. A total of 73 parts of a mixture of acids having a neutral equivalent of 198 wasobtained of which 13.4 parts were dibasic acids having a neutral equivalent of 101.
Example 4" The same procedure was followed-in the caustic fusion of a glyceridie ester; namely the cyanohydroxy derivative of tallow. Thus, .75 parts of that derivative yielded 755 parts of-a mixture-of acids having a neutral equivalent of 200, of which 13.6parts were dibasic acids having a-neutral equivalent of 101 and including azelaic and sebacic acids.
Essentially the same products were obtained by the fusion of the cyanohydroxy derivative of brown grease.
Similarly, the fusion of 77.5 parts of the cyanohydroxy acids of tallow gave rise-to 77 parts of a mixture of acids having a neutral equivalent of 178, of which 16.8 parts were dibasic acids having a neutral equivalent of 99.5.
I claim:
1. The process for preparing saturated aliphatic mono carboxylic and dicarboxylic acids which comprises reacting molten caustic alkali, at a temperature from about 200 C. to about 400 C., with a compound from the class consisting. of (a) saturated aliphatic acids containing 16 to 22 carbon atoms and (b) esters of said acids and saturated aliphatic alcohols containing 1 to 4 hydroxyl groups, said compound also containing in its acid chain a group having the formula OH CN (311 rcthereafter dissolving the resultant mixture of salts in water; and acidifying the resultant aqueous solution to precipitate said monocarboxylic and dicarboxylic acids, and isolating said acids.
2. The process for preparing saturatedaliphatic monocarboxylic and dicar'b'oxylic acids which comprises re- 'a'cting'molten caustic alkali, at a temperature from'aboitt 310 C. to about 340 C., with a saturated aliphatic acid containing 16 to 22 carbon atoms and also containing a cyano group and an hydroxyl group on vicinal carbon atoms; thereafter dissolving the resultant mixture of salts in water; and acidifying the resultant aqueous solution to precipitate said saturated aliphatic monocarboxylic and dicarboxylic acids and isolating said acids.
3. The process of claim 2 in which said acid is cyanohydroxystearic acid.
1. The process for preparing saturated aliphatic monocarboxylic and dicarboxylic acids which comprises rcacting molten caustic alkali, at a temperature from about 310 C. to about 340 C. with a lower alkyl ester of a saturated aliphatic acid which contains 16 to 22 carbon atoms and which also contains a cyano group and an hydroxyl group on vicinal carbon atoms; thereafter dissolving the resultant mixture of salts in water; and acidifying the resultant aqueous solution to precipitate said saturated aliphatic monocarboxylic and dicarboxylic acids and isolating said acids.
5. The process of claim 4 in which said ester is a lower alkyl ester of cyano-hydroxystearic acid.
6. The process for preparing saturated aliphatic monobasic and dibasic acids which comprises reacting molten caustic alkali, at a temperature from about 200 to about 400 C., with a glyceridic ester of a saturated aliphatic acid which contains 16 to 22 carbon atoms and which also contains a cyano and an hydroxyl group on vicinal carbon atoms; thereafter dissolving the resultant mixture of salts in water; and acidifying the resultant aqueous solution to precipitate said saturated aliphatic monocarboxylic and dicarboxylic acids and isolating said acids.
7. The process of claim 6 in which said glyceridic ester is a glyceridic ester of cyano-hydroxystearic acid.
Lane Ian. 1, 1952 Logan Ian. 13, 1953
Claims (1)
1. THE PROCESS FOR PREPARING SATURATED ALIPHATIC MONOCARBOXYLIC AND DICARBOXYLIC ACIDS WHICH COMPRISES REACTING MOLTEN CAUSTIC ALKALI, AT A TEMPERATURE FROM ABOUT 200*C. TO ABOUT 400*C., WITH A COMPOUND FROM THE CLASS CONSISTING OF (A) SATURATED ALIPHATIC ACIDS CONTAINING 16 TO 22 CARBON ATOMS AND (B) ESTERS OF SAID ACIDS AND SATURATED ALIPHATIC ALCOHOLS CONTAINING 1 TO 4 HYDROXYL GROUPS, SAID COMPOUND ALSO CONTAINING IN ITS ACID CHAIN A GROUP HAVING THE FORMULA
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US2580931A (en) * | 1950-07-22 | 1952-01-01 | Du Pont | Production of sebacic acid |
US2625558A (en) * | 1950-08-23 | 1953-01-13 | Kessler Chemical Co Inc | Process for making organic compounds |
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US2580931A (en) * | 1950-07-22 | 1952-01-01 | Du Pont | Production of sebacic acid |
US2625558A (en) * | 1950-08-23 | 1953-01-13 | Kessler Chemical Co Inc | Process for making organic compounds |
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