US2974152A - Preparation and isolation of alkali metal and ammonium sulfonates of long chain carboxylic acids - Google Patents
Preparation and isolation of alkali metal and ammonium sulfonates of long chain carboxylic acids Download PDFInfo
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- US2974152A US2974152A US580728A US58072856A US2974152A US 2974152 A US2974152 A US 2974152A US 580728 A US580728 A US 580728A US 58072856 A US58072856 A US 58072856A US 2974152 A US2974152 A US 2974152A
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- alkali metal
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- carboxylic acids
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- 150000001735 carboxylic acids Chemical class 0.000 title claims description 7
- 229910052783 alkali metal Inorganic materials 0.000 title description 15
- 150000001340 alkali metals Chemical class 0.000 title description 15
- -1 ammonium sulfonates Chemical class 0.000 title description 6
- 238000002955 isolation Methods 0.000 title description 4
- 238000002360 preparation method Methods 0.000 title description 4
- 238000000034 method Methods 0.000 claims description 17
- 239000002253 acid Substances 0.000 claims description 14
- 150000007513 acids Chemical class 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical class [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 15
- 239000000203 mixture Substances 0.000 description 13
- 150000003839 salts Chemical class 0.000 description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
- 235000019270 ammonium chloride Nutrition 0.000 description 9
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 8
- 238000006277 sulfonation reaction Methods 0.000 description 8
- DIORMHZUUKOISG-UHFFFAOYSA-N sulfoformic acid Chemical class OC(=O)S(O)(=O)=O DIORMHZUUKOISG-UHFFFAOYSA-N 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 6
- 238000006386 neutralization reaction Methods 0.000 description 6
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 229920006395 saturated elastomer Polymers 0.000 description 5
- 239000011780 sodium chloride Substances 0.000 description 5
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 5
- 238000010992 reflux Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 4
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 3
- 239000003599 detergent Substances 0.000 description 3
- 239000003085 diluting agent Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000012065 filter cake Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 150000003871 sulfonates Chemical class 0.000 description 3
- TWJNQYPJQDRXPH-UHFFFAOYSA-N 2-cyanobenzohydrazide Chemical compound NNC(=O)C1=CC=CC=C1C#N TWJNQYPJQDRXPH-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 235000021360 Myristic acid Nutrition 0.000 description 2
- TUNFSRHWOTWDNC-UHFFFAOYSA-N Myristic acid Natural products CCCCCCCCCCCCCC(O)=O TUNFSRHWOTWDNC-UHFFFAOYSA-N 0.000 description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000001632 sodium acetate Substances 0.000 description 2
- 235000017281 sodium acetate Nutrition 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- RNAMYOYQYRYFQY-UHFFFAOYSA-N 2-(4,4-difluoropiperidin-1-yl)-6-methoxy-n-(1-propan-2-ylpiperidin-4-yl)-7-(3-pyrrolidin-1-ylpropoxy)quinazolin-4-amine Chemical compound N1=C(N2CCC(F)(F)CC2)N=C2C=C(OCCCN3CCCC3)C(OC)=CC2=C1NC1CCN(C(C)C)CC1 RNAMYOYQYRYFQY-UHFFFAOYSA-N 0.000 description 1
- 235000021357 Behenic acid Nutrition 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 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 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical class [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910001514 alkali metal chloride Inorganic materials 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 229940101006 anhydrous sodium sulfite Drugs 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 229940116226 behenic acid Drugs 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000002704 decyl 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])* 0.000 description 1
- KFEVDPWXEVUUMW-UHFFFAOYSA-N docosanoic acid Natural products CCCCCCCCCCCCCCCCCCCCCC(=O)OCCC1=CC=C(O)C=C1 KFEVDPWXEVUUMW-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 150000004668 long chain fatty acids Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000002960 margaryl 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])[H] 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- POULHZVOKOAJMA-UHFFFAOYSA-N methyl undecanoic acid Natural products CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000001421 myristyl 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])[H] 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- 125000001400 nonyl 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])[H] 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl 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])[H] 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 235000003441 saturated fatty acids Nutrition 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 235000015424 sodium Nutrition 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
- C07C309/01—Sulfonic acids
- C07C309/02—Sulfonic acids having sulfo groups bound to acyclic carbon atoms
- C07C309/03—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
- C07C309/17—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing carboxyl groups bound to the carbon skeleton
Definitions
- the present invention relates to the preparation of alkali metal and ammonium salts'of long' chain sulfocarboxylic acids and, particularly, to an improved method of neutralizing said acids and isolating the resulting salts. It is known that long chain canboxylic acids are con- I verted into a-sulfocarboxylic acids by means of sulfonating agents such as chlorosulfonic acid (U.S.P.' 2,360,968;
- boxylic acids are isolated in the form of their salts and, to this end, it is conventional procedure to form the salts by neutralization of the reaction mixture with a strong alkali-such as sodium hydroxide or the like. Neutralization may be effected either before or after removal of the solvent or diluent or'by' pouring the sulfonation mixture onto the alkali.
- carboxylic acids contemplated for sulfonation herein may be typified by the following general formula:
- the free sulfocar-' alkali metal chlorides or a ammonium .chlorides but R- -C;OOH in which' R is an aliphatic chain of at lease 6 ca rbon atoms such as hexyl, heptyl, octyl, nonyl, decyl, dodecyhj tetradecyl, heptadecyl and the like.
- Acids which are. especially suitable are those which are commonly used in detergent manufacture such as myristic acid,,palmitic acid and the like.
- the sulfocarboxylic acids neutralized accordingtoour procedure are formed according to conventional sulfonation processes involving the use of a sulfonating agent such as sulfur trioxide orchlorosulfonic acid in an inert.- diluent or solvent such as carbon tetrachloride or the like. Any method of sulfonation used in the prior art may be employed to produce the crude mixtures subsequently. neutralized and isolated; by us in the'form of the desired, sulfonates. -The reaction between the crude sulfonation mixture?
- a sulfonating agent such as sulfur trioxide orchlorosulfonic acid in an inert.- diluent or solvent such as carbon tetrachloride or the like.
- the alkali metal or ammonium chloride is preferably: effected by adding'a saturated aqueous solution of: theselected chloride to the 'hot SUllfOl'lfltlOIl mixturewhile stirring; After the reaction has subsided, a suitablet organic solvent such as acetone, methylethylketone'oru any other inert organic solvent which is misciblefwitht j water may be added to -expedite the filtration'of the sulfonates which have been formed.
- a suitablet organic solvent such as acetone, methylethylketone'oru any other inert organic solvent which is misciblefwitht j water may be added to -expedite the filtration'of the sulfonates which have been formed.
- the quantity of alkali metal or ammonium chloride used is about equivalent: to the amount of sulfurtrioxide or 'itsequivalent usedfor' sulfonation.”
- I 5 3 The chlorides which are employed rnayib': any ofthefi e prefer to use sodium, potassium or ammonium chloride ii Each of these operates smoothly to effect the desired con-- version of the sulfocarboxylic acids to the corresponding alkali metal or ammonium sulfonates with formation of HCl.
- Example II A 2-liter round bottom three-necked flask equipped with a dropping funnel with attached CaCl tube, a stirrer and reflux eondenserwith an attached CaCl tube (the reflux condenser being attached to a Barrett receiver) was charged with 228.3 grams (1.0 mol) of myristic acid and 400 mls. of dry carbon tetrachloride.
- Example 111 e The procedure was the same as in Example 11 except that the acid employed was palmitic and the chloride was ammonium chloride.
- R is an alkyl group of at least 6 carbon atoms
- the improvement which comprises isolating the resulting sulfocarboxylic acid as a sulfonate selected from the class consisting of alkali metal and ammonium sulfonates by adding to the crude reaction mixture an aqueous solution of a'salt selected from the class consisting of alkali metal and ammonium chloride and isolating the resulting solid product.
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Detergent Compositions (AREA)
Description
u Lam.
United States ice A ,;;;,f;,,
PREPARATION AND ISOLATION OF ALKALI METAL AND AMMONIUM SULFONATES 'OF LONG CHAIN CARBOXYLIC ACIDS No Drawing. Filed Apr. 26, 1956, Ser. No. 580,728
6 Claims. (Cl. 260-400) The present invention relates to the preparation of alkali metal and ammonium salts'of long' chain sulfocarboxylic acids and, particularly, to an improved method of neutralizing said acids and isolating the resulting salts. It is known that long chain canboxylic acids are con- I verted into a-sulfocarboxylic acids by means of sulfonating agents such as chlorosulfonic acid (U.S.P.' 2,360,968;
.U.S.P. 2,413,199) in the presence or absence of solvents or diluents (U.S.P. 2,448,370) and with or withoutcatalysts (U.S.P. 2,268,443). boxylic acids are isolated in the form of their salts and, to this end, it is conventional procedure to form the salts by neutralization of the reaction mixture with a strong alkali-such as sodium hydroxide or the like. Neutralization may be effected either before or after removal of the solvent or diluent or'by' pouring the sulfonation mixture onto the alkali.
The detergent properties of long chain sulfocarboxylic acids and their use in the preparation of detergents made it mandatory that changes be effected in the conventional neutralization process in order to realize the salts in a pure form and in a substantially dry condition. It was, therefore, recommended that crude mixtures of sulfonated long chain carboxylic acids be neutralized in vacuum (U.S.P. 2,613,218) or by means of anhydrous sodium sulfite in dry form or suspended in organic solvents and,
in this connection, reference may be made to U.S.P. 2,511,043 and 2,607,801. Other proposals were that neutralization of the sulfonated material be effected with solid sodium bicarbonate or lime (U.S.P. 2,511,043), potassium hydroxide in methanol (It. 433,792) or sodium acetate and sodium carbonate (JACS 75, 4859 (1953)). In any case, either alkali or the salts of weak acids were used for the neutralization of the crude mixture. Actually, sodium acetate or Na SO will presumably also give monosodium salts but alkali metal chlorides are much cheaper.
We have now discovered that the isolation of alkali metal and ammonium sulfonates of long chain sulfocarboxylic acids can be greatly improved while obtaining such salts in a substantially pure form and dry condition by neutralizing crude sulfonated long chain carboxylic acids in inert solvents with alkali metal or ammonium chlorides to selectively effect salt formation with the sulfo but not with the carboxy group.
It is an object of the invention to provide an improved method of isolating alkali metal and ammonium sulfonates of long chain carboxylic acids from crude sulfonation mixtures by means of alkali metal and ammonium chlorides.
It is a further object of the present invention to effect such neutralization with saturated aqueous solutions of alkali metal and ammonium chlorides.
It is a further object of the present invention to isolate the alkali metal and ammonium sulfonates in a substantially pure condition and dry form.
The carboxylic acids contemplated for sulfonation herein may be typified by the following general formula:
Usually, the free sulfocar-' alkali: metal chlorides or a ammonium .chlorides but R- -C;OOH in which' R is an aliphatic chain of at lease 6 ca rbon atoms such as hexyl, heptyl, octyl, nonyl, decyl, dodecyhj tetradecyl, heptadecyl and the like. Acids which are. especially suitable are those which are commonly used in detergent manufacture such as myristic acid,,palmitic acid and the like. I Y
The sulfocarboxylic acids neutralized accordingtoour procedure are formed according to conventional sulfonation processes involving the use of a sulfonating agent such as sulfur trioxide orchlorosulfonic acid in an inert.- diluent or solvent such as carbon tetrachloride or the like. Any method of sulfonation used in the prior art may be employed to produce the crude mixtures subsequently. neutralized and isolated; by us in the'form of the desired, sulfonates. -The reaction between the crude sulfonation mixture? and the alkali metal or ammonium chloride is preferably: effected by adding'a saturated aqueous solution of: theselected chloride to the 'hot SUllfOl'lfltlOIl mixturewhile stirring; After the reaction has subsided, a suitablet organic solvent such as acetone, methylethylketone'oru any other inert organic solvent which is misciblefwitht j water may be added to -expedite the filtration'of the sulfonates which have been formed. The quantity of alkali metal or ammonium chloride used is about equivalent: to the amount of sulfurtrioxide or 'itsequivalent usedfor' sulfonation." I 5 3 The chlorides which are employed rnayib': any ofthefi e prefer to use sodium, potassium or ammonium chloride ii Each of these operates smoothly to effect the desired con-- version of the sulfocarboxylic acids to the corresponding alkali metal or ammonium sulfonates with formation of HCl.
A peculiar feature of our procedure resides in the factv that the alkali metal or ammonium chloride, while forming a salt with the sulfo group, is indifferent to and does: not react wit-h the carboxy group. As a conseque'nce,. the salt formation which the sulfocarboxylic acid under-- goes is selective in that it involves only the sulfo group.. This greatly expedites the isolation of the sulfonates in a;
substantially pure form and dry condition.
It is known from the literature that the conventional? i monosulfonation of long chain fatty acids results in the introduction of the sulfo group on the a-carbon atom, i.e.",. that attached to the carboxy group. Inasmuch as only the sulfo group is converted to a salt group when satu-- rated fatty acids are treated according to our procedure; the compounds obtained will have the following structural 750 mls. of carbon tetrachloride and 284 grams of stearic acid were heated to boiling. Without heating, 70 mls. of freshly distilled chlorosulfonic acid were added, with stirring, within 10 minutes. After refluxing for another minutes, the evolution of HCl subsided.
To the hot sulfonation mixture were added 62 grams of a saturated aqueous solution of sodium chloride, within five minutes, without heating. After stirring for another 10 minutes, 3.7 liters of acetone were added, the mixture cooled, filtered and washed again with acetone. A brownish-white, well-crystallized product is formed which is; pure enough for most purposes. purified by suspending with stirringin 2.5 liters of acetone, filtering, washing, and warming the filter cake to 90 in four liters of 6 N acetic acid over a period of 30 minutes. After cooling, filtering, washing, and drying, a white light powder is formed. Yield: 200 grams;,M.P. 292-293. (dccomp). Analysis: S found 7.73%, theoretical 8.3%; acid no. found 137, calc. 145.1.
Example II A 2-liter round bottom three-necked flask equipped with a dropping funnel with attached CaCl tube, a stirrer and reflux eondenserwith an attached CaCl tube (the reflux condenser being attached to a Barrett receiver) was charged with 228.3 grams (1.0 mol) of myristic acid and 400 mls. of dry carbon tetrachloride.
To the warm, but not refluxing, stirrred mixture were added, dropwise, over a period of 20 minutes, 72 mls. (1.1 mols) of chlorosulfonic acid. The mixture was refiuxed with stirring for an additional four hours. The reaction mixture was poured into a 2-liter beaker, and 200mls. of a saturated salt solution were added in a thin stream while the mixture was stirred quite rapidly. The mixture was cooled, filtered and the filter cake suspended in 500 mls. of acetone. The mixture was again filtered, sucked dry and the filter cake recrystallized from 2 liters of water. The precipitate was filtered otf, washed with 200 mls. of acetone and air dried. The yield was 175 grams and the product melted above 300 C.
Example 111 e The procedure was the same as in Example 11 except that the acid employed was palmitic and the chloride was ammonium chloride.
Modifications of the invention will occur to persons skilled in the an and we, therefore, do not intend to be It can further be am-1,152 r a .4 limited in the patent granted except as necessitated by the appended claims.
We claim:
1. In the process of producing u-SlllfOCfil'bOXYliC acids by treating with a sulfonating agent, a carboxylic acid of the formula:
in which R is an alkyl group of at least 6 carbon atoms, the improvement which comprises isolating the resulting sulfocarboxylic acid as a sulfonate selected from the class consisting of alkali metal and ammonium sulfonates by adding to the crude reaction mixture an aqueous solution of a'salt selected from the class consisting of alkali metal and ammonium chloride and isolating the resulting solid product.
2. The process as defined in claim 1, in which the chloride is added in the form of a saturated aqueous solution.
3. The process as defined in claim 1, in which the chloride is added in the form of an aqueous saturated solution and the chloride is used in an amount substantially equivalent to the amount of sulfonating agent.
4. The process as defined in claim 1, wherein the acid is stearic and the chloride is sodium chloride.
5. The process as defined in claim 1, wherein the acid is myristic acid and the salt is sodium chloride.
6. The process as defined in claim 1, wherein the acid is docosanoic acid and the salt is sodium chloride.
OTHER REFERENCES Weil: J. Am. Chem. Soc. 75, 2526-2527 (1953).
Claims (1)
1. IN THE PROCESS OF PRODUCING A-SULFOCARBOXYLIC ACIDS BY TREATING WITH A SULFONATING AGENT, A CARBOXYLIC ACID OF THE FORMULA:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US580728A US2974152A (en) | 1956-04-26 | 1956-04-26 | Preparation and isolation of alkali metal and ammonium sulfonates of long chain carboxylic acids |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US580728A US2974152A (en) | 1956-04-26 | 1956-04-26 | Preparation and isolation of alkali metal and ammonium sulfonates of long chain carboxylic acids |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2974152A true US2974152A (en) | 1961-03-07 |
Family
ID=24322289
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US580728A Expired - Lifetime US2974152A (en) | 1956-04-26 | 1956-04-26 | Preparation and isolation of alkali metal and ammonium sulfonates of long chain carboxylic acids |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US2974152A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3725441A (en) * | 1968-04-29 | 1973-04-03 | Lubrizol Corp | Acylating agents, their salts, and lubricants and fuels containing the same |
| US3888918A (en) * | 1972-12-07 | 1975-06-10 | Ethyl Corp | Process for reacting a sultone with a non-basic alkali metal, alkaline earth metal or ammonium halide salt in an anhydrous system |
| US5587500A (en) * | 1993-09-17 | 1996-12-24 | The Chemithon Corporation | Sulfonation of fatty acid esters |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2098114A (en) * | 1935-10-17 | 1937-11-02 | Procter & Gamble | Process for sulphonating alcohols |
-
1956
- 1956-04-26 US US580728A patent/US2974152A/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2098114A (en) * | 1935-10-17 | 1937-11-02 | Procter & Gamble | Process for sulphonating alcohols |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3725441A (en) * | 1968-04-29 | 1973-04-03 | Lubrizol Corp | Acylating agents, their salts, and lubricants and fuels containing the same |
| US3888918A (en) * | 1972-12-07 | 1975-06-10 | Ethyl Corp | Process for reacting a sultone with a non-basic alkali metal, alkaline earth metal or ammonium halide salt in an anhydrous system |
| US5587500A (en) * | 1993-09-17 | 1996-12-24 | The Chemithon Corporation | Sulfonation of fatty acid esters |
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