US2396969A - Production of alpha-halogenated keto acids - Google Patents
Production of alpha-halogenated keto acids Download PDFInfo
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- US2396969A US2396969A US558073A US55807344A US2396969A US 2396969 A US2396969 A US 2396969A US 558073 A US558073 A US 558073A US 55807344 A US55807344 A US 55807344A US 2396969 A US2396969 A US 2396969A
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- 238000004519 manufacturing process Methods 0.000 title description 12
- 150000004715 keto acids Chemical class 0.000 title description 10
- 239000002253 acid Substances 0.000 description 37
- 235000014113 dietary fatty acids Nutrition 0.000 description 22
- 239000000194 fatty acid Substances 0.000 description 22
- 229930195729 fatty acid Natural products 0.000 description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 21
- -1 alphahalogenated keto fatty acids Chemical class 0.000 description 17
- 229910052500 inorganic mineral Inorganic materials 0.000 description 16
- 239000011707 mineral Substances 0.000 description 16
- 239000000243 solution Substances 0.000 description 16
- 239000000463 material Substances 0.000 description 14
- 230000001590 oxidative effect Effects 0.000 description 13
- 238000000034 method Methods 0.000 description 12
- 238000007254 oxidation reaction Methods 0.000 description 11
- 239000000344 soap Substances 0.000 description 11
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 10
- 150000003944 halohydrins Chemical class 0.000 description 10
- 150000007513 acids Chemical class 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 150000004665 fatty acids Chemical class 0.000 description 9
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 9
- 125000000468 ketone group Chemical group 0.000 description 9
- 230000003647 oxidation Effects 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 8
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 8
- 239000007858 starting material Substances 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- 125000004432 carbon atom Chemical group C* 0.000 description 7
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 5
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 5
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 5
- 229930194542 Keto Natural products 0.000 description 5
- 239000005642 Oleic acid Substances 0.000 description 5
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- JUCAMRNDACLKGY-UHFFFAOYSA-N 2-oxooctadecanoic acid Chemical class CCCCCCCCCCCCCCCCC(=O)C(O)=O JUCAMRNDACLKGY-UHFFFAOYSA-N 0.000 description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- 235000021355 Stearic acid Nutrition 0.000 description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 4
- 229910052794 bromium Inorganic materials 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 4
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000008117 stearic acid Substances 0.000 description 4
- NDYMYSCKMCQILW-UHFFFAOYSA-N 2-oxodocosanoic acid Chemical class CCCCCCCCCCCCCCCCCCCCC(=O)C(O)=O NDYMYSCKMCQILW-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 235000021357 Behenic acid Nutrition 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000008346 aqueous phase Substances 0.000 description 3
- 229940116226 behenic acid Drugs 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000010504 bond cleavage reaction Methods 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 230000007017 scission Effects 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- JHWIEAWILPSRMU-UHFFFAOYSA-N 2-methyl-3-pyrimidin-4-ylpropanoic acid Chemical compound OC(=O)C(C)CC1=CC=NC=N1 JHWIEAWILPSRMU-UHFFFAOYSA-N 0.000 description 2
- DPUOLQHDNGRHBS-UHFFFAOYSA-N Brassidinsaeure Natural products CCCCCCCCC=CCCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-UHFFFAOYSA-N 0.000 description 2
- URXZXNYJPAJJOQ-UHFFFAOYSA-N Erucic acid Natural products CCCCCCC=CCCCCCCCCCCCC(O)=O URXZXNYJPAJJOQ-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- XENVCRGQTABGKY-ZHACJKMWSA-N chlorohydrin Chemical compound CC#CC#CC#CC#C\C=C\C(Cl)CO XENVCRGQTABGKY-ZHACJKMWSA-N 0.000 description 2
- DPUOLQHDNGRHBS-KTKRTIGZSA-N erucic acid Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-KTKRTIGZSA-N 0.000 description 2
- 230000026030 halogenation Effects 0.000 description 2
- 238000005658 halogenation reaction Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- KJDGFQJCHFJTRH-YONAWACDSA-N 16-Ketoestradiol Chemical class OC1=CC=C2[C@H]3CC[C@](C)([C@H](C(=O)C4)O)[C@@H]4[C@@H]3CCC2=C1 KJDGFQJCHFJTRH-YONAWACDSA-N 0.000 description 1
- NUMXHEUHHRTBQT-AATRIKPKSA-N 2,4-dimethoxy-1-[(e)-2-nitroethenyl]benzene Chemical compound COC1=CC=C(\C=C\[N+]([O-])=O)C(OC)=C1 NUMXHEUHHRTBQT-AATRIKPKSA-N 0.000 description 1
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 1
- SSZWWUDQMAHNAQ-UHFFFAOYSA-N 3-chloropropane-1,2-diol Chemical compound OCC(O)CCl SSZWWUDQMAHNAQ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- OFHCOWSQAMBJIW-AVJTYSNKSA-N alfacalcidol Chemical compound C1(/[C@@H]2CC[C@@H]([C@]2(CCC1)C)[C@H](C)CCCC(C)C)=C\C=C1\C[C@@H](O)C[C@H](O)C1=C OFHCOWSQAMBJIW-AVJTYSNKSA-N 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001845 chromium compounds Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000001475 halogen functional group Chemical group 0.000 description 1
- 230000002140 halogenating effect Effects 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- CUILPNURFADTPE-UHFFFAOYSA-N hypobromous acid Chemical class BrO CUILPNURFADTPE-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 239000006188 syrup Substances 0.000 description 1
- 235000020357 syrup Nutrition 0.000 description 1
- 235000021081 unsaturated fats Nutrition 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
Definitions
- Patented Mar. 19, 1946 1 UNITED STATE s PATENT OFFICE PRODUCTION OF ALP KETO A HA-HALOGENATED cms No Drawing. Application October 10, 1944,
- the present invention relates to the production of alpha-halogenated keto acids. More particularly the present invention relates to a novel process for the production of alphaehalogenated keto acids from unsaturated fats, esters, and fatty acids.
- halo hydrin acids may then be oxidized under the conditions set forth in U. S. application Serial No. 467,810, filed December 3, 1942, to mono halo'keto acids in quantitative yields.
- the fatty chains contained in the starting materials to be processed in accordance with this invention may contain one or more unsaturated linkages.
- keto compounds resulting from theoxidation of the hydroxyl groups in these configurations tend to be oxidatively and/or l5 hydrolytically split in the vicinity of the keto verting olefinic fatty. substances to the corresponding mono halogenated keto. substances.
- a further object is to obtain commercially practical yields of mono halogenated keto fatty and then treating the halo hydrin compounderides may be 'used.';In fact, any fatty materialwith an aqueous chromic acid solution at moderate temperatures so as to oxidize the hydroxy groupings in the -fatty material to form keto groupings.
- the water contained in the aqueous chromic acid solution causes the formation of two separate phases, one containing the chromic acid, and the othercontainin'g the fatty material, thus efiectively regulating the progress of the reaction and avoiding oxidative scission of' the fatty material 'even at somewhat elevated temperatures.- During the course of the reaction.
- the mixture is vigorously agitatedto bring. about intimate contact of the chromic acid and fatty
- the reaction is com-'- pleted, the resulting halogenated keto fatty ma-' terials are separated from the spent chromic acid solution and are purified.
- fatty acids suitable for use as starting materials in the practice of this invention are exemplified in .oleic acid, palmitoleic, myristoleic, erucic and other like acids.
- mixtures of acids and/or acid 'glyccapable of being saponified. either during the reaction to form thihal'o hydrinacid' or prior to the reaction is .suitable for use as'a starting material.
- Unsaturated acids havingzmore than one double bond such as linoleic and linolenic I and hydroxy unsaturated acids-such asricinoleic may also be used although since these commonly occurring acids have their double bonds in close proximity the yields of halogenated keto acids are somewhat low.
- the fatty acids are initially converted to a-potassium or sodium soap by admixture with an aqueous solution of sodium or potassitun hydroxide.
- the aqueous-chromic acid oxidizing reagent may conveniently be an aqueous solution of NazCrzO-1 and HzSOl.
- the chromic acid solution may be prepared from any other hexavalent' chromium compound such as CI'QQ; KzCrzOv or NazCrO4 and any other oxidation-stable mineral acid such as HNO; or HaPO4.
- the water content of the oxidizing reagent must be suiiiciently high to cause 'the'chromic acid to form a separate phase when mixed with the hydroxylated fatty material. In general. the
- halogenated ketonic fatty products when recovered are characterized by sharp melting points.
- the hexavalent chromium compound should preferably be present in approximately 10% excess over the' quantity stoichiometrically required to oxidize the fatty material to be treated; however, in those cases in which side reactions are to be expected-for instance in the treatment of materials containing closely spaced double bonds,
- the oxidizing mixture may also have incorporated therewith a small amount of an oxidation resistant mutual solventfor the fatty material and thechromic acid, such as acetic acid.
- an oxidation resistant mutual solventfor the fatty material and thechromic acid such as acetic acid.
- the. solvent is used in a relatively small amount, insuflicient to cause the aqueous and fatty material phases to merge,
- this is carried out by intimatelymixing and agitating the halo hydrin fatty starting material with the aqueouschromic acidsolut'ion.
- the agitation is continued throughout the duration of the reaction to avoid local stagnation and to insure ture is maintained sufficiently high to'effect the oxidation of the hydroxyl groups in the fatty material to keto groups at an economic rate but is not maintained'so' high asto causeoxidative scission of the fatty chains.
- ternperatures between about 20- and about 80 C.
- reaction'mixture is diluted with water.
- the oxidized fatty material is separated from the spent acids and salts- Thereafter the occluded acids and-salts are washed out of the oxidized; 7 fatty product by means of aqueous washing soluing to 5 a 10% excess of chlorine gas'was passed through the resulting soapy solution with stirring.
- the excess hypochlorous acid was destroyed by the addition of sodium bisulfite solution until litmus paper was no longer bleached and then the aqueous solution was carefully acidified with sulfuric acid.
- the fatty acids that separated were dissolved in benmile. This benzene solution was extracted with water until it was neutral. The moisture and sol-' vent were removed by distillation.
- the temperationsfand the washed product is recrystallized by means of organiesolvents.
- the aqueous washing agent should preferably be slightly acid in order to prevent the formation of and to break up any complexes or soaps formed by the fatty material with the chromic ions resulting from the oxidation reaction.
- a process for the production of alpha mono halogenated keto acids which comprises reacting a water-soluble soap of an unsaturated higher fatty acid containing a fatty chain of at least 8 carbon atoms with a member of the group consisting of hypobromous and hypochlorous acids to produce a halo hydrin fatty acid and thereafter oxidizing the halo hydrin fatty acid to an alpha mono halogenated keto acid by reacting .the same with a hexavalent chromium compound in the presence of an oxidation-resistant mineral acid and in the presence of sufiicient water to insure maintenanceof an aqueous phase separate from the halo hydrin fatty acid.
- a process for the production of alpha mono halogenated keto stearic acid which comprises.
- a process for the production of alpha mono halogenated keto stearic acid which comprises reacting a water-soluble soap of oleic acid with a member of the group consisting of hypobromous and hypochlorous acids to produce halo hydrin stearic acid and thereafter oxidizing the halo hydrin stearic acid to alpha mono halopresence of suflicient water to insure maintenance of an aqueous phase separate from the halo hydrin fatty acid.
- a process for the production of alpha mono halogenated keto hehenic acid which comprises reacting a water-soluble soap of erucic acid with a member of the group consisting of hypobromous and hypochlorous acids to produce halo hydrin behenic acid and thereafter oxidizing the halo hydrin behenic acid to alpha mono halogenated keto behenic acid by reacting the same with a hexavalent chromium compound in-the presence of an oxidation-resistant mineral acid and in the resence of sufiicient water to insure maintenance of an aqueous phase separate from the halo hydrin fatty acid.
- a process for the production of alpha mono halogenated keto acids which comprises reacting a water-soluble soap of an unsaturated higher fatty acid containing fatty chains of at least 8 genated keto stearic acid by reacting the same with a hexavalent chromium compound in the presence of an aqueous solution of an oxidationresistant mineral acid, the mineral acid being present to the extent of between 25 and 75% based on the total weight of mineral acid and water present in the reaction mixture.
- a process for the production of alpha mono halogenated keto behenic acid which comprises reacting a water-soluble soap of erucic acid with a member of the group consisting of hypobromous and hypochlorous acids to produce halo hydrin beh'enic acid and thereafter oxidizing the halo hydrin behenic acid to alpha mono halogenated keto behenic acid by reacting the same with a hexavalent chromium compound in the presence of an aqueous solution of an oxidationresistant mineral acid, the mineral acid being present to the extent of between 25 and 75% based on the total weight of mineral acid and water present in the reaction mixture.
- a process for the production of alpha mono halogenated keto acids which comprises dissolving a soap of an unsaturated higher fatty acid containing fatty chains of at least 8 carbon atoms in water, passing a halogen selected from the group consisting of chlorine and bromine into the soap-water solution to produce a halo hydrin fatty acid and thereafter oxidizing the halo hydrin fatty acid by reacting the sam with a hexavalent chromium compound in the presence of an aqueous solution of an oxidation-resistant I mineral acid, the mineral acid being present to the extent of between 25 and based on the total weight of mineral acid and .water present in the reaction mixture.
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- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
. material phases.
Patented Mar. 19, 1946 1 UNITED STATE s PATENT OFFICE PRODUCTION OF ALP KETO A HA-HALOGENATED cms No Drawing. Application October 10, 1944,
Serial No. 558,073
8 Claims. (Cl. 260-406) The present invention relates to the production of alpha-halogenated keto acids. More particularly the present invention relates to a novel process for the production of alphaehalogenated keto acids from unsaturated fats, esters, and fatty acids.
In application Serial No. 511,594, filed November '24, 1943, there are disclosed various alphahalogenated keto fatty acids and a process 'for preparing them involving halogenating keto fatty acids. As thus pointed out, such a halogenation tends to produce a, '-dihalo compounds and only under conditions of restrained halogenation is it possible to confine the same to only one alpha carbon to a relatively small extent. a e
In accordance with the present invention, how ever, it has been discovered that if the unsaturated fatty acids are treated with hypohalous acids, 1. e. hypochlorous and hypobromous acids,
to produce halo hydrin acids, the halo hydrin acids may then be oxidized under the conditions set forth in U. S. application Serial No. 467,810, filed December 3, 1942, to mono halo'keto acids in quantitative yields.
Accordingly. it is 'an object of this invention to provide a readily-controlled process for coninvention, there may be employed any fatty acids containing fatty chains of 8 or more carbon atoms and having an olefine linkage preferably separated from the carboxyl carbon by at least 2 carbon atoms in the chain and fatty materials containing such acids in a form capable of being readily'con'verted to'soaps so that they may be brought into intimate contact inaqueous solution with the hypohalous acid. The fatty chains contained in the starting materials to be processed in accordance with this invention may contain one or more unsaturated linkages. Preferably when more than one unsaturated linkage is present, they are separated by at least two carbon atoms inthe chain as closer proximity of the double bonds gives rise to the formation of closely adjacent hydroxy groups which are likely to promote oxidation and/or hydrolytic scission at these points. Starting materials con,-
taining-closely spaced double bonds willresult in somewhat reduced yields of 'keto fatty substances, sincethe keto compounds resulting from theoxidation of the hydroxyl groups in these configurations tend to be oxidatively and/or l5 hydrolytically split in the vicinity of the keto verting olefinic fatty. substances to the corresponding mono halogenated keto. substances.
A further object .is to obtain commercially practical yields of mono halogenated keto fatty and then treating the halo hydrin compounderides may be 'used.';In fact, any fatty materialwith an aqueous chromic acid solution at moderate temperatures so as to oxidize the hydroxy groupings in the -fatty material to form keto groupings. The water contained in the aqueous chromic acid solution causes the formation of two separate phases, one containing the chromic acid, and the othercontainin'g the fatty material, thus efiectively regulating the progress of the reaction and avoiding oxidative scission of' the fatty material 'even at somewhat elevated temperatures.- During the course of the reaction.
the mixture is vigorously agitatedto bring. about intimate contact of the chromic acid and fatty When the reaction is com-'- pleted, the resulting halogenated keto fatty ma-' terials are separated from the spent chromic acid solution and are purified.
As starting materials in the process of this groups.
The fatty acids suitable for use as starting materials in the practice of this invention are exemplified in .oleic acid, palmitoleic, myristoleic, erucic and other like acids. In place of the acids themselves, mixtures of acids and/or acid 'glyccapable of being saponified. either during the reaction to form thihal'o hydrinacid' or prior to the reaction is .suitable for use as'a starting material. Unsaturated acids havingzmore than one double bond such as linoleic and linolenic I and hydroxy unsaturated acids-such asricinoleic may also be used although since these commonly occurring acids have their double bonds in close proximity the yields of halogenated keto acids are somewhat low. I
Referring to the production of the halo hydrin acids from the fatty acids, preferably the. fatty acids are initially converted to a-potassium or sodium soap by admixture with an aqueous solution of sodium or potassitun hydroxide.
Thereafter chlorine or' bromine is passed into the resulting soapy solution while cooling, the chlorineor bromine being used in slight excess, 1. e. up to about 25%. The excess chlorine or bromine is then destroyedv as by the addition of sodium hydrin acid is oxidized to the halogenated keto acid as hereinafter 'set forth. 1
Referring to the aqueous-chromic acid oxidizing reagent, this may conveniently be an aqueous solution of NazCrzO-1 and HzSOl. However, the chromic acid solution may be prepared from any other hexavalent' chromium compound such as CI'QQ; KzCrzOv or NazCrO4 and any other oxidation-stable mineral acid such as HNO; or HaPO4. The water content of the oxidizing reagent must be suiiiciently high to cause 'the'chromic acid to form a separate phase when mixed with the hydroxylated fatty material. In general. the
The halogenated ketonic fatty products when recovered are characterized by sharp melting points.
Specific examples of the practice of this invention will now be described, all parts given being by weight. The sodium dichromate referred to in the examples was in all cases the hydrate NazClzOm2Ha0. v
- Example I :57 g. of oleic acid were converted to the potase slum soap by stirring with a solution of 23 g. of
potassium hydroxide to 3 l..of water. After coolamount of sulfuric acid contained in the oxidizing reagent should be between about 25% and about 75% of the combined amounts of water and sulfuric acid present therein. The hexavalent chromium compound should preferably be present in approximately 10% excess over the' quantity stoichiometrically required to oxidize the fatty material to be treated; however, in those cases in which side reactions are to be expected-for instance in the treatment of materials containing closely spaced double bonds,
the excess should beincreased to 50% or higher. The optimum proportions are best determined by preliminary experiment on the particular fatty materialto be processed, bearing'in mind the general consideration abovesetfor'th.
In addition to the chromic acid, the oxidizing mixture may also have incorporated therewith a small amount of an oxidation resistant mutual solventfor the fatty material and thechromic acid, such as acetic acid. However, preferably the. solvent is used in a relatively small amount, insuflicient to cause the aqueous and fatty material phases to merge,
Referring to the oxidation'process, this is carried out by intimatelymixing and agitating the halo hydrin fatty starting material with the aqueouschromic acidsolut'ion. The agitation is continued throughout the duration of the reaction to avoid local stagnation and to insure ture is maintained sufficiently high to'effect the oxidation of the hydroxyl groups in the fatty material to keto groups at an economic rate but is not maintained'so' high asto causeoxidative scission of the fatty chains. In general ternperatures between about 20- and about 80 C.
- will accomplish these results depending on the nature of the fatty starting material. The length of time required for. the completion of the" reaction will vary with the nature of the starting ma-- terial, the composition of the oxidizing agent,
and thetemperature at which the reaction is conducted. Ingeneralbetween about 5 and about B-hours will be required:
At the conclusion of the; oxidation reaction,
the reaction'mixture is diluted with water. and
the oxidized fatty material is separated from the spent acids and salts- Thereafter the occluded acids and-salts are washed out of the oxidized; 7 fatty product by means of aqueous washing soluing to 5 a 10% excess of chlorine gas'was passed through the resulting soapy solution with stirring. After standing for 1 to 2 hours, the excess hypochlorous acid was destroyed by the addition of sodium bisulfite solution until litmus paper was no longer bleached and then the aqueous solution was carefully acidified with sulfuric acid. The fatty acids that separated were dissolved in benmile. This benzene solution was extracted with water until it was neutral. The moisture and sol-' vent were removed by distillation. The yield of contact between the aqueous chromic acid-phase and the fatty starting material. The temperationsfand the washed productis recrystallized by means of organiesolvents. The aqueous washing agent should preferably be slightly acid in order to prevent the formation of and to break up any complexes or soaps formed by the fatty material with the chromic ions resulting from the oxidation reaction. F y
The practice of this invention as above outlined results in excellent yields of halogenated .ketonic fatty products free of undesired lay-products.
product (a golden syrup) was 60 g. (91%). -Neutral equivalent 345; I. V. 0.6. To a suspension of 50 grams of the oleic acid chlorhydrin in cc.
of 50% aqueous sulfuric acid a solution of 15 grams of'sodium 'dichromate'in 35 cc. of water .was added with stirring over a period of V hour at 50-55 C." Stirring was continued at this temperature for 7 /2 hours more. The reaction mixture was diluted 'witha large volume of water. After two layers had formed, the upper oily layer was separated from the water layer. The oily layer was dissolved in 2 volumes of a petroleum solvent and this solution was then boiled with 2 parts-of 18% hydrochloric acid based on the weight of the oil for 1 hour. After removal of the aqueous acid layer, thepetroleum solvent was removed by distillation. The residual oil weighed 49grams, equivalent to a yield of 98%. Neutral equivalent 337. v Theory 337.
Example If zene solution was extracted with water until it was neutral. The moisture and solvent were removed by distillation. The yield of chlorohydrin acid was 58 g. (94%). To a suspension of 58 g. of the chlorohydrin acid in 290 cc.-.of 50% sulfuric 81d,13 solution of 12.8 g. of sodium dichromate injz'i' cc. 'of water was added with stirring over a period of hour at 50 to 55 C. Stirring was continued at this temperature for 7% hours and the solids collected on 'afllter. The solids were dissolved in a petroleum solvent and boiled with 18% hydrochloric acid for 1 hour. After removal of the water layer, the solvent was removed by distillation. The residual oil which weighed 56 g.-(9'7% yiefd) was dissolved in petroleum ether and chilled at -1'1 overnight. The solid was collected on a filter and reclailled. A
second crop was obtained. Total yield of recrystallized material was 40 g. Neutral equivalent 388. Theory 889.
taining a fatty chain of at least 8 carbon atoms with a. member of the group consisting of hypobromous and hypochlorous acids to produce a halo hydrin fatty acid and thereafter oxidizing the halo hydrin fatty acid with an aqueous chromic acid solution to an alpha mono halogenated keto acid.
-2. A process for the production of alpha mono halogenated keto acids which comprises reacting a water-soluble soap of an unsaturated higher fatty acid containing a fatty chain of at least 8 carbon atoms with a member of the group consisting of hypobromous and hypochlorous acids to produce a halo hydrin fatty acid and thereafter oxidizing the halo hydrin fatty acid to an alpha mono halogenated keto acid by reacting .the same with a hexavalent chromium compound in the presence of an oxidation-resistant mineral acid and in the presence of sufiicient water to insure maintenanceof an aqueous phase separate from the halo hydrin fatty acid.
3. A process for the production of alpha mono halogenated keto stearic acid which comprises.
reacting a water-soluble soap of oleic acid with a member of the group consisting of hypobromous and hypochlorous acids to produce a halo hydrin of stearic acid and thereafter oxidizing the halo hydrin stearic acid to alpha mono halogenated keto stearic acid by reacting the same with a hexavalent chromium compound in the presence of an oxidation-resistant mineral acid and in the carbon atoms with a member oi the group consisting of hynobromous and hypochlorous acids to produce a halo hydrin fatty acid and thereafter oxidizing the halo hydrin fatty acid by reacting the same with a hexavalent chromium compound in the presence of an aqueous solution of an oxidation-resistant mineral acid, the mineral acid being present to the extent of between and 75% based on the total weight of mineral acid and water present in the reaction mixture.
6. A process for the production of alpha mono halogenated keto stearic acid ,which comprises reacting a water-soluble soap of oleic acid with a member of the group consisting of hypobromous and hypochlorous acids to produce halo hydrin stearic acid and thereafter oxidizing the halo hydrin stearic acid to alpha mono halopresence of suflicient water to insure maintenance of an aqueous phase separate from the halo hydrin fatty acid.
4. A process for the production of alpha mono halogenated keto hehenic acid which comprises reacting a water-soluble soap of erucic acid with a member of the group consisting of hypobromous and hypochlorous acids to produce halo hydrin behenic acid and thereafter oxidizing the halo hydrin behenic acid to alpha mono halogenated keto behenic acid by reacting the same with a hexavalent chromium compound in-the presence of an oxidation-resistant mineral acid and in the resence of sufiicient water to insure maintenance of an aqueous phase separate from the halo hydrin fatty acid.
5. A process for the production of alpha mono halogenated keto acids which comprises reacting a water-soluble soap of an unsaturated higher fatty acid containing fatty chains of at least 8 genated keto stearic acid by reacting the same with a hexavalent chromium compound in the presence of an aqueous solution of an oxidationresistant mineral acid, the mineral acid being present to the extent of between 25 and 75% based on the total weight of mineral acid and water present in the reaction mixture.
- 7. A process for the production of alpha mono halogenated keto behenic acid which comprises reacting a water-soluble soap of erucic acid with a member of the group consisting of hypobromous and hypochlorous acids to produce halo hydrin beh'enic acid and thereafter oxidizing the halo hydrin behenic acid to alpha mono halogenated keto behenic acid by reacting the same with a hexavalent chromium compound in the presence of an aqueous solution of an oxidationresistant mineral acid, the mineral acid being present to the extent of between 25 and 75% based on the total weight of mineral acid and water present in the reaction mixture.
8. A process for the production of alpha mono halogenated keto acids which comprises dissolving a soap of an unsaturated higher fatty acid containing fatty chains of at least 8 carbon atoms in water, passing a halogen selected from the group consisting of chlorine and bromine into the soap-water solution to produce a halo hydrin fatty acid and thereafter oxidizing the halo hydrin fatty acid by reacting the sam with a hexavalent chromium compound in the presence of an aqueous solution of an oxidation-resistant I mineral acid, the mineral acid being present to the extent of between 25 and based on the total weight of mineral acid and .water present in the reaction mixture.
DONALD PRICE. FRANCIS J. SPRU'LES.
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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US2557159A (en) * | 1947-01-13 | 1951-06-19 | Howard M Teeter | Halogenated unsaturated higher fatty acids and derivatives |
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US2557159A (en) * | 1947-01-13 | 1951-06-19 | Howard M Teeter | Halogenated unsaturated higher fatty acids and derivatives |
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