CA1060444A - .beta.-SULFO-PROPIONIC ACID COMPOUNDS AND PROCESS - Google Patents
.beta.-SULFO-PROPIONIC ACID COMPOUNDS AND PROCESSInfo
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- CA1060444A CA1060444A CA233,420A CA233420A CA1060444A CA 1060444 A CA1060444 A CA 1060444A CA 233420 A CA233420 A CA 233420A CA 1060444 A CA1060444 A CA 1060444A
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- carbon atoms
- hydrogen
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- alkyl
- beta
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/02—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements
- C07D295/027—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements containing only one hetero ring
-
- 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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/04—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D233/06—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to ring carbon atoms
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- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Coloring (AREA)
- Detergent Compositions (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE: New .beta.-sulfo-propionic acid compounds and a process for their manufacture by reaction of alcohols, acid amides or amines with .beta.-sulfo-carboxylic acid anhydrides.
The compounds are textile assistants, e.g. washing, cleaning or wetting agents, dishwashing detergents, hair shampoos, emulsifiers, flotation agents, plasticizers and starting materials for th manufacture of such agents, as well as for the manufacture of dyes and pesticides.
The compounds are textile assistants, e.g. washing, cleaning or wetting agents, dishwashing detergents, hair shampoos, emulsifiers, flotation agents, plasticizers and starting materials for th manufacture of such agents, as well as for the manufacture of dyes and pesticides.
Description
The invention relates to new ~-sulfo-propionic acid compounds and a process for their manufacture by reaction of alcohols, acid amides or amines with ~-sulfo-carboxylic acid .
anhydrides.
The reaction of ~-sulfo-propionic anhydride with methanol, ammonia or amines to give the corresponding ester or amide, respecti-vely, is disclosed in J. Amer. Chem. Soc., 62 (1940), 2,395 - 2,397.
We have found new ~-sulfo-propionic-acid compounds of the formula - 2 2 / ~ R \ O R o ~ C-C ~ ~3-C-C-C 2-5~ Z
where R is a straight-chain, alkyl of 4 to 26 carbon atoms, alkenyl of 4 to Z6 carbon atoms, alkylcarbonyl of 4 to 26 carbon 3 atoms, aralkyl of 7 to 26 carbon atoms, or 2-ethylhexyl, the ~ndividual R2'~ may be identical or different and each is hydrogen or alkyl of 1 to 4 carbon atoms, R3 is oxygen or R4 where R4 is , : -N-hydrogen, alkyl of 1 to 4 carbon atoms or hydroxyethyl, Z is , a hydrogen ion, , , ~/C~2-C~
H2N ~
~: C}12- H2 , : .
i an alkali metal ion or R5-N-H , the individual R5's being identical .~ R5 J. or different and each being an alkyl of 1 to 26 carbon atoms, hydroxyethyl or hydrogen, n is O or an integer from 1 to 100, and if n is 0,Rl and R3 may also together be H
: H Cl --- C - R6 N ~ / N -R H
~7 1 ~
L
- ^i^. .
R6 being hydroxyethyl or hydrogen and R2 ha~ing the meanings given above, and the above radicals being optionally further be substituted by one or more substituents selected f~om carboxylic acid amide, cyano, nitro, chlorine, bromine, carbalkoxy and acy-lamido each of 2 to 4 carbon atoms, or alkyl and alkoxy each of 1 to 4 carbon atoms.
Further, we have found that ~-sulfo-propionic acids of the formula C-~ ~ R3-c-c-cH2-so3H Ia 1~ ~ n R
wherein R is a straight-chain, alkyl of 4 ,to 26 carbon atoms, alkenyl of 4 to 26 carbon atoms, a~kylcarbonyl of 4 to 26 carbon atoms, aralkyl of 7 to 26 carbon atoms or 2-ethylhexyl , the individual R~'s may be identical or different and each is hydrogen or alkyl of 1 to 4 carbon atoms, R3 is oxygen or R4 where R4 is -N-hydrogen, alkyl of 1 to 4 carbon atoms or hydroxyethyl, n is 0 or an integer from 1 to 100 and if n is 0, Rl and R3 may also together be H---C C R6 , where R6 is hydroxyethyl or , .
N N
.~, \C/
, R 2 hydrogen and R has the above meanings, may be obtained advanta-geously by reaction of alcohols, acid amides or amines with acid anhydrides if alcohols, acid amides or amines of the formula ; 30 L.
.... ~
1060444 ooæO 30,756 ~ H R ~
Rl ~-C C ~ R3~H II
wher-e Rl, R2, R3 and n have the above meanings, are reacted with ~-sulfocarboxylic acid anhydrides of the formula .~ ~
. O
where R2 ha~ the above meanings~
Further, we have found that an advantageous embodiment of the process is to react the resulting ~-sulfo-propionic acids Ia with alkali, morpholine or a base of the formula . R5 - N IV
where R5 has the above meanin~s, to give ~-sulfo-propionic acid ~ compounds Or the formula 3 ~ H R2\ O R2 ~
1 Rl _ ~ C-C ~ R -C-C2CH2 S 3 y~ Ib 1 in which Rl, R2, R3 and n have the above meaning~ and Y is - ",CH2 CH~ R5 ~ CH2-CH2 , an alkali metal ion or R5-N-H~, where R
the individual R5's may be identical or different and each is an aliphatic radical or hydrogen.
Where sulfo-propionic anhydride, dodecyl alcohol and morpholine . are used, the reaction may be represented by the following equation:
C12H25 OH ~ olc-cH2-cH2-so2 ~~~~ C12H25 o-C-CH2-CH2-S3H
~ H2-C~
+HN ~ O
-3~ /
10609~44 CH C~
Cl2H25-OCO-C~2-CH2-S03 H2N o Compared to the state of the art, the process of the invention gives a large number of new ~-sulfo-propionic acid compounds, in the form of esters, monoacylamides and diacylamides, simply and economically and in good yield and purity.
The starting materials II and III can be reacted in stoichiometric amounts or in excess (of one material), preferably in a ratio of from 0.5 to 2.5 moles of starting material II per mole of starting material III. Preferred starting materials II, III and IV and accordingly preferred products I, Ia and Ib are those wherein R is advantageously straight-chain alkyl of 8 to 24, and especially of 12 to 24, carbon atoms,especially straight-chain alkenyl of 8 to 24, carbon atoms,advantageously straight-chain alkylcarbonyl of 8 to 24, and especially of 12 to 24, carbon atoms, advantageously aralkyl of 10 to 24 and especially of 10 .~ to 18 carbon atoms, in particular nonylphenyl, isooctylphenyl or octylphenyl, or 2-ethylhexyl, the individual R 's may be : 20 identical or different and each is hydrogen or alkyl of 1 to 4 carbon atoms, R is oxygen or R where R is hydrogen, alkyl of . N
1 to 4 carbon atoms or hydPoxyethyl, Z is a hydrogen ion, ,,/CH2-CH~ , . H2N~ ~ O , - .
C~ 2 - C H2 . sodium or potassium or R5 , where the individual R5's may be .' R5-N-H
identical or different and each is advantageously an alkyl of 8 to 24, and especially of 12 to 24, carbon atoms, hydroxyethyl or hydrogen, n is 0 or an integer from 2 to 80, and if n is 0, and R3 may also together be H
. H-C______c_~6 N N -c/
. ~. 4 1060444 oOzO 30,756 where R6 is hydroxyethyl or hydrogen and R2 has the above meaningsO
The above radicals can further be substituted by groups and/or atoms which are inert under the reaction conditions, eOgO
carboxylic acid amide, cyano, nitro, chlorine, bromine, carb-alkoxy and acylamido each of 2 to 4 carbon atoms, or alkyl and alkoxy each of 1 to 4 carbon atomsO It is also possible, and advantageous, to react mixtures of ~traight-chain alcohols, e.g.
those obtained from the oxo ~ynthesis, and further process the resulting mixtureR of products I directly9 eOg~ to give surfactants.
This i~ economically advantageous because it saves isolating the individual alcohols from the mixtures, which in most cases is a laborious operation entailing heavy lossesO A rurther range of very valuable alcohols for the reaction with the sulfocarboxylic acid anhydride is obta;ned by oxyalkylation of straight-chain alcohols with epoxides, e.g. ethylene ox;de and/or propylene oxide, which are reacted with the alcohols in the ratio of rrom 1 to 100 moles Or alkylene oxide or a mixture o~ the epoxides per mole Or alcohol. If mixtures of amines, e~gO fatty amines such as laurylamine, are u~ed as starting materials, mixtures of the sul~onates of these amines with the corresponding ~-sui~opropionic acid amides are obtainedO
Examples of suitable starting materials II are n-butyl , alcohol, 2-ethylhexanol, n-octanol, decanol, dodecanol, tetra-decyl alcohol, octadecyl alcohol, stearic acid ethanolamide, the glycol half-e~ter o~ lauric acid, octylphenol, nonylphenol and dodecylphenol; butylamine, decylamine, dodecylamine, octa-decylamine, dibutylamine, methylbutylamine, methylbenzylamine, methyltetradecylamine and N-ethanol-N-butylamine; n-nonanol, n-undecanol, tridecanol, pentadecanol, hexadecanol, heptadecanol, 3o n-tetracosanol, octadecenyl alcohol 9 2-undecyl-5-hydroxyethyl-imidazoline5 n-nonylamine, oleylamine, 2-ethylhexylamine, hexa-cosanol and lauric acid ethanolamide; the above alcohols oxyalkylated with 2, 3, 4, 5, 25, 80 or 100 moles of ethylene oxide or propylene oxide or moles of ethylene oxide and propylene oxidé (in :: ~5-.
-- ~060444 oOzO 30,756 the ratio Or rrom 0.1 to 20 moles o~ propylene oxide per mole Or ethylene oxide), e~gO nonylphenyl tris oxyethyl alcohol C9H19 ~ ~CH2 CH2 ~ H ; and appropriate mixturesO
Possible starting materials III are ~-sulfopropionic anhydride, ~-sulfopivalic anhydride and the anhydride of 2-ethylhexane-1-sulfonic acid-2-carboxylic acidO
The reaction is a~ a rule carried out at from 0 to 120C, prererably from 20 to 90C, under atmospheric or superatmospheric pressure, continuously or batchwiseO Preferably, no solvent is used. However it iæ also possible to use organic solvents which are inert under the reaction conditions, such as chlorohydro-carbons, e~g. ethylene chloride and chloroform, cyclic ethers, ' e~g. dioxane and tetrahydrofuran, and aliphatic or aromatic hydrocarbons, eOgc toluene, heptane and petroleum etherO
The reaction may, eOgO, be carried out as ~ollows:
the appropriate etarting material II i8 added to the sulfocarb-oxy}ic acid anhydride III, optionally in a solvent, whilst ~tirring well~ The mixture is then kept ror a further 2 to 3 hours at the reaction temperature. The product is isolated by conventional methods, eOgo by distillationO It is, however, more advantageous to neutralize the sulfonic acid Ia which has been .7 formed with bases IV, alkali or morpholine and to isolate the product Ib by conventional methods, eOgO by crystallization ~rom suitable solvents such as alkanols, e.~. ethanol and isobutanol, ~ halohydrocarbons, eOgO ethylene chloride and chloroform, tetra-- ~ hydrofuran, acetone, ethyl acetate and diethyl ether. Where amines : ~
~ II are used, neutralization is conveniently efrected by using an ., :
. ~ -appropriate excess Or amine II. In general, the neutralization is . ~ .
~0 effe¢ted at ~rom 0 to 80C, under atmospheric or superatmospheric ~; pressure, continuously or batchwise, over the course Or ~rom 0.1 to 12 hours, using from 1 to 4, prererably from 106 to 3, equiva-~ lents of base per mole o~ product Ia. Preferred bases are sodium '~ -6-~ .
1060444 oOzO 30,756 and potassium compoundsg especially sodium hydroxide and potassium hydroxide, morpholine9 ammonia, pr;mary, secondary or tertiary alkylamines of 1 to 26, advanta~eously of 1 to 4 or 8 to 24, carbon atoms per alkyl group, eOgO dimethylamine, methylamine, trimethylamine, triethylamine, diethylamine, mono-ethylamine, propylamine, dipropylam;ne, tripropylamine, dibutyl-amine, butylamine, tr;butylamine, nonylamine, dinonylamine, tri-nonylamine, tetracosylamine, isopropylamine, diisopropylamine, triisopropylamine, stearyIamine, distearylamine and tristearyl-amine, and amine~ containing hydroxyethyl groups, eOgO ethanolamine,diethanolamine, triethanolamine, butyldiethanolamine and dimethyl-ethanolamineO After neutralization, the salt ;s isolated by con ~entional methods, eOgO by filtrationO
The new products I which can be manufactured by the process Or the invention are text;le assistants, eOgO washing, cleansing or wetting agents, dishwashing detergents, hair shampoos, emulsi-~iers, ~lotation agents, plasticizers and ~aluable starting materials ror the manufacture of such a~sistants, as well as ror the manufacture of dyes and pesticidesO Thus, with all products of the examples which ~ollow, eOgO with a mixture Or sodium ,' (dodecyl-dioxyethyl propionate)-B-sulfonate and sodium (tetra-decyl-dioxyethyl propionate)-B-sulfonate (in the ratio Or ~
a very good wetting erfect on cellulos;c material and a very good ~ detergent action when laundering cotton fabrics and washing J~ woolen article~, impregnated with oli~e oil or ~ineral oil, i8 achieved at concentrations o~ only from 10 to.100 parts per 1,000 parts o~ water~ Furthermore, all the products Or the examples which follow, eOgO the mixture of sodium (dodecyl-tris-oxyethyl propionate)-~-sulfonate and ~odium (octadecyl-tri~-oxyethyl propio-nate)-R-sulfonate tin the ratio of 1 : 1) can be used in dish-washing detergents of moderate foaming power, having, eOg., the following composition:
5 parts o~ diethanQlamine alkylbenzenesulfonate ~06~444 O.Z0 30,756 5 parts of nonylphenol condensed with 10 moles of ethylene oxide 5 parts of ~odium (dodecyl/octadecyl-tris-oxyethyl propionate)-~-sulfonate (1 : 1) 5 parts Or isopropanol 5 parts of tetrapotassium pyropho~phate 75 parts of water In the Examples which follow, parts are by weight.
29.6 parts Or n-butanol are added to a melt o~ 5405 parts o~ ~-sulropropionic anhydride at 65C, whilst stirring~ A~ter stirring ror a rurther two hours at 70C, the sulfonic acid I
which i6 formed is neutralized by adding 51.7 parts Or butyl-diethanolamine. 122 parts (8~.8% Or theory) of butyldiethanol-, ammonium ~butyl propionate)-~-~ulfonate are obtained as a brown ; oil. n20 ~ 1.47120 ~ 130 parts o~ 2-ethylhexanol are added ~lowly to a melt of `! 163 parts o~ ~-sul~opropionic anhydride at 75C A~ter stirring for a further three hours at 80C, the mixture i~ adjusted to pH
~ 5 with 90 parts Or 50 per cent strength by weight sodium hydroxide ¦ ~olution at 50C, whilst ~tirring. Sodium (2-ethylhexyl propionate)-A-sulronate is obtained in the rorm of a 64 per cent strength by weight paste which is readily water-soluble. Yield: 265 parts (9005% of theory)0 n20 - 1.4589.
(a) 130 parts Or dodecyl alcohol are added slowly to a melt Or 95 parts of ~-sulPopropionic anhydride at from 75 to 80C, whilst ¦; stirring and slightly cooling the mixture. A~ter stirring ror a ¦ 3 further three hours at 85C~ 225 parts of (dodecyl propionate)-~-sulronic acid Or melting point 36 - 38C (arter recry~tallization rom ethylene chloride) are obtained.
:
106~444 o ~z o 30,756 (b) 28.6 parts of morpholine are added to 9608 parts of the sul~onic acid I at 40C, whilst stirringO The mixture is diluted with 100 parts of ethylene chloride and stirred for 2 hours at 60C. After adding 800 parts of petroleum ether, the morpholinium (dodecyl-propionate)-~-sulfonate which has crystallized out is rilt;ered of~ and recrystallized from ethanolO Melting point 74 -77C; yield: 100 parts (81~5% of theory)0 65.5 parts of ~-sulfopivalic anhydride are introduced into 74.5 parts of dodecyl alcohol at 25C, whil~t stirring. When the - exothermic reaction ha~ ended, the mixture is slowly warmed to 70C and stirred at this temperature for 3 hours~ The (dodecyl pivalate)-~-sulfonic acid is ob~ained in the form of a yellow ; oil Or n20 = lo 45630 37 parts of morpholine are added slowly to the product Io Arter dilution with 250 part~ o~ petroleum ether, the mixture i8 stirred ~or one hourO ~he ~uspension obtained is cooled and the product is then filtered Or~ and re¢rystallized ~rom acetoneO
Melting point 7005 ~ 72C; yield-146 parts (74o2%-0~ theory) 20 Or morpholinium (dodecyl pivalate)~ ulfonate.
,~ 48D5 parts of a mixture o~ straight-chain alcohols, con-l taining 2705% by weight Or nonyl alcohol, 12% by weight o~ decyl !
alcohol and 6005% of undecyl alcohol are added to a melt o~ 41 parts of ~-sulfopropioni~ anhydride at 65C, whilst stirring.
~ ~:
ll~ After stirring for a further three hours at 70C, the mixture is ~ .:,pr, cooled and neutralized-with 48 parts o~ 25 per cent strength by weight sodium hydroxide solution at 30QC. A water-soluble paste '~ containing 137 parts (100% o~ theory) of sodium (nonyi, decyl and 30 undecyl propionate)-~-sulfonate of melting point 280 - 285C
i (with decomposition) (after recrystallization rrom acetone) is obtainedO The ratio of the esters corresponds to the ratio Or the alcohols used.
'~
1060444 o zO 30,756 64 parts o~ a mixture of straight-chain alcohols con-taining 2805% by weight of dodecanol, 27% by weight of tri-decanol, 23% by weight of tetradecanol and 210 5% b~ wei~ht of pentadecanol are added to a melt of 41 parts of sulfopropionic anhydride at ~rom 70 to 80C After stirring for a further three hours at 70C, the sulfonic.acid.I, which is in.the ~orm of a dark brown oil, is neutralized by adding 2605 parts Or 50 per cent strength by weight sodium hydroxide solution.
130 parts (100% of theory) o~ ~odium.(tridecyl, dodecyl, tetradecyl and pentadecyl propionate)-~-sulfonate o~ nD =
1 4613 are obtained. The ratio of the esters corresponds to the ratio of the alcohols usedO
78 parts Or a mixture of n-hexadecyl alcohol and n-octadecyl alcohol (2: 1) are added to a melt of 41 parts Or ~-sul~opropionic anhydride, whilst stirring~ Arter ~tirring ~or a further three hours at 75C, the brown melt is.taken up in 350 parts of ethylene chloride and 29 parts o~ morpholine 20 are added whilst stirring at from 50 to 70~0 The ethylene ¢hloride is distilled off under. reduced.pressure .and the re~i-due i8 recrystallized ~rom ethanolO 142 parts (96% Or theory) o~ morpholinium (hexadecyl/octadecyl propionate)~-sulronate are obtained in the form o~ light brown: crystals. rlelting point 76 ~ 80Co The ratio of the esters corresponds to the ratio o~ the alcohols used.
68.5 parts o~ a fatty alcohol mixture containing 41%
by weight of dodecanol, 30% by weight of tetradecanol, 18% by 30 weight of hexadecanol and 11% by weight Or octadecanol are added to a melt of 41 parts of sulfopropionic anhydride at from 60 to 70C J whilst stirring After stirring ror a further three hours, the sulfonic acid T iS obtained as a O.Z0 30,756 brown oil which is neutralized by adding 26~4 part~ o~ 50 per cent strength by weight sodium hydroxide solution at 30C~
Precipitation with acetone gives 93 parts of sodium (dodecyl, tetradecyl, hexadecyl and octadecyl/propionate)-~-sulfonate) a~ white cry~tals which give a clear solution in waterO Melting point ~00C (with decomposition)0 The ratio of the esters corres-pond~ to the ratio o~ the alcohol~ used.
99.5 parts o~ a mixture,of n-dodecyl alcohol and n-tetra-decyl alcohol (55.5 : 4505) oxyethylated with 3 mole~ of ethylene oxide are added to a melt of 41 parts of R-~ulfo-propionic anhy-dride at from 50 to 70C~ whilst stirring. A~ter stirring for a ~ùrther three hours at 70C, 2806 parts,or morpholine are added to the mixture at ~rom 40 to 70C and the batch i8 stirred for a ~urther ~ hours. 159 part~ (94% o~ theory) Or morpholinlum ~do~ecyl/tetradecyl-tri~-oxyethyl propionate)-~-sulronabe are obtiined as a light brown pasteO n20 - 1.4598~.The.lratio o~ the e~torB ¢orre~pond~ to the ratio Or the.alcohols used.
6~.5 parts o~ ~-sul~opi~alic anhydride,are introduced.in~o 133 parts of a mixture o~ n-dodecyl-..and n~tetradecyl-tris-oxyethyl alcohol (55 ; 45) at from 60 to 70C. 198 parts (a practically quantitative yield) o~ the ~ulfonic acid-I are obtained:as a red-brown oil-o~ nD = 1.4613.
The mixture i3 neutralized by adding ~9.5 parts Or 50 per .
cent strength by weight sodium hydroxide solution. 237 parts ~, (a practically.quantitative yield) of sodium,(dodecyl/tetradecyl-tris-oxyethyl pivalate)-~-sulfonate are obtained,as a 91.6 per cent strength.a~ueous solution. The ratio.of the e~ters corresponds ~0 to the ratio of the alcohols u~ed.
9.5 parts o~ sulfopropionic anhydri~e are-added to 227-parts o~ a mixture.o~ straight-chain alcohol~, containin~.65% by weight ,.~
~C~60444 OOZo 30,756 of hexadecanol and 35% by weight of octadecanol, which has been oxyethylated with 80 moles o~ ethylene oxide. After stirring for a rurther three hours at rrom 75 to 80C, the (propionic acid e~ter)-sulronic acids I are obtained as a brown oil (n50 _ 1.4617).
Thi~ is neutralized by adding 236 parts of water and 10 parts o~
50 per cent strength by weight sodium hydroxide solution at from 30 to 40C. 482 parts of the sodium (propionic acid ester)-~-sulronate based on the above alcohol mixture are obtained as an aqueous paste. The ratio of the esters corresponds to the ratio Or the alcohols used.
, EXAMPLE 12 378 part~ Or n-nonanol which has been oxyalkylated with moles Or ethylene oxide and 2 moles Or propylene oxide are added to a melt of 129 parts of ~-sul~opropionic anhydride at from 70 to 80C, whilst stirring. Arter stirring for a further two hours at 80~, 508 parts (a practically quantitative yield) o~ (nonylpentaoxyethyl propionate)-~-sulfonic acid,are obtained ~ as a brown oil (n30 = 104590)o The product i8 nçutralized by ', adding 57 parts of 50 per cent strength by weight sodium hydroxide ~olution and 250 parts of water, 815 parts (a practically quanti-I tative yield) of the sodium salt are obtained in the form o~ a 1 66 per cent strength aqueous solutionO
j EXAMPLE 13 i ~ 106 parts of n tetracosanol are added to a melt Or 41 parts ~-sulfopropionic anhydride at from 60 to 70C,,whilst stirring.
1 A~ter stirring for a further four hours at 70C, 147 parts (a ¦~ practically quantitative yield) of (tetracosyl propionate)-~-f sul~oni,c acid are obtained as a brown oil (n50~= 104537). Arter ;~ dilution with 260 parts of water, the mixture is neutralized with 24 parts o~ 50 per cent strength by weight sodium hydroxide soiution.
430 parts (a practically quanti~ative yield) or the sodium salt are obtained in the rorm Or a 35 per cent strength aqueous oil.
`:
OOZo 30,756 78 parts Or n-octadecenyl alcohol are added to 41 parts Or sulfopropionic anhydride at 60C, whilst stirring~, Arter ~tirring ror a further three hours at 70C, 119 parts (a prac-tically quantitative yield) of (octadecenyl propionate)-~-~ulfonic acid are obtained as a brown oil (nD = 1.4550). 45 parts Or triethanolamine are added at 70Co The mixture is stirred for a further 2 hours at 70C, 163 parts (a practically quantitative yield) Or pasty triethanolamine salt are obtained.
1180 5 parts of nonylphenol which has been oxyalkylated with 4 moles Or ethylene oxide are added to 41:parts of,~-sulropro-pionic anhydride at 70C, whilst stirring. After stirring for a rurther two hours at 75C, 4208 parts Or dibutylamine, are added at ~rom 40 to 60C and the mixture is stirred ror a rurther 2 hour~ at 70C. 192 part~ (97% o~ theory) Or dibutylan~onium ~nonylphenyl-tetraoxyethyl propionat:e)-~-~ulronate.are: obtained , a~ a brown oil (n20 - 1.4904).
~,, EXANPI,E 16 13.6 parts of~ ~-sulfopro.pionic anhydride .are added at 70C, ~, whilst stirring, to 130.6 parts of .-isooctylphenol which ba~ been oxyalkylated with 25 moles Or ethylene oxideO Arter 3.hours at 70C, 144 D2 parts (a practically quantibative yield) of product .' I (n20 ~ 1.4847) are obtained" A~ter adding.2.70 parts o~ water, 12 parts Or 50 per cent strength by weight sodium hydroxide solution , are introduced and the mixture is stirred for 2 hours at 40~.;, 426 parts (a practically quantitative yield) o~ sodium (isooctyl-'~ phenyl propionate)~ ul~onate:are obtained as. a light brown 35 per cent strength aqueous oil.
;- i34 parts Or 2-undecyl-5-hydroxyethyl-imidazoline are added , to 68 part~ o~ ~-sulropropionic.anhydride at 80~ he mixture is stirred ror a further 4 hours at 80C, givin~;.l98.part~ (98% Or `- ~060444 0OZo 309756 theory) of N-(2-undecyl-5-hydroxyethyl~imidazolinyl)-propionic acid-R-sulfonic acidO
54O5 parts of ~ulfopropionic anhydride are added to a solution Or 120 part~ of n-nonylamine in 250 parts Or ethylene chloride at 40C, whil~t stirringO After stirring for a further two hours at 45C, the suspension is riltered and the crystalline product is recrystallized from ethylene-chlorideO 86 parts ' (71.4% of theory) of nonylammonium (propionyl-nonylamide)-~-sulfonate are obtained as colorless crystals of melting point / 167 ~ 169Co :, EXAMPLE 19 41 parts of sulfopropionic anhydride are added to a solution :, of 160 parts Or oleylamine in 200,parts Or ethylene,chloride at from 50 to 60C. Arter one hour, 25 parts Or 50,per cent strength ,~ by weight ~odium hydroxide so}ution are added to the red-brown ,~ oil obtained, and the mixture is stirred for,one hour at 80C.
A~ter cooling, the suspension is riltered and the,re~idue is heated with acetone at 56C,ror halr an hourO 167 parts (650~%
.~ 20 of theory) of sodium (propionyl-oleylamide)-~-sulfonate Or melting point 304 - 309C are obtainedO
3~ 144 parts o~ di-(2-ethylhexyl)-,amine are added to 41 parts Or sulfopropionic anhydride at-70 - B0C, whilst ~tirringO After ~: stirring for a further two hour~ at 130C, 176,parts (70% Or : '~
: ~ theory) Or di-(2-ethylhexyl)-ammoniwn (propionyl-di-(2-ethylhexyl)-, ~ amide)-~-sulfonate are obtained as a brown. oil of nD s 1.4724.
~, 243 parts of lauric acid ethanolamide are added to 136 parts 30 of ~-sulfopropionic anhydride at from 70 to 80C, whilst stirring.
After stirring for a furkher three hours at 80C, 379 parts (practically the quantitative yield) Or (propionyl-lauroylethanol-amide)~ ulfonic acid of n50 = 1.4719 are obtained.
106044~ oOz. 30,756 After dilution with 250 parts of water, the mixture is neutralized with 120 parts of 50 per cent strength by weight sodium hydroxide solution. 743 parts (a practically quantitative yield) of the sodium salt are obtained in the form of a 55 per cent strength white paste.
~15-
anhydrides.
The reaction of ~-sulfo-propionic anhydride with methanol, ammonia or amines to give the corresponding ester or amide, respecti-vely, is disclosed in J. Amer. Chem. Soc., 62 (1940), 2,395 - 2,397.
We have found new ~-sulfo-propionic-acid compounds of the formula - 2 2 / ~ R \ O R o ~ C-C ~ ~3-C-C-C 2-5~ Z
where R is a straight-chain, alkyl of 4 to 26 carbon atoms, alkenyl of 4 to Z6 carbon atoms, alkylcarbonyl of 4 to 26 carbon 3 atoms, aralkyl of 7 to 26 carbon atoms, or 2-ethylhexyl, the ~ndividual R2'~ may be identical or different and each is hydrogen or alkyl of 1 to 4 carbon atoms, R3 is oxygen or R4 where R4 is , : -N-hydrogen, alkyl of 1 to 4 carbon atoms or hydroxyethyl, Z is , a hydrogen ion, , , ~/C~2-C~
H2N ~
~: C}12- H2 , : .
i an alkali metal ion or R5-N-H , the individual R5's being identical .~ R5 J. or different and each being an alkyl of 1 to 26 carbon atoms, hydroxyethyl or hydrogen, n is O or an integer from 1 to 100, and if n is 0,Rl and R3 may also together be H
: H Cl --- C - R6 N ~ / N -R H
~7 1 ~
L
- ^i^. .
R6 being hydroxyethyl or hydrogen and R2 ha~ing the meanings given above, and the above radicals being optionally further be substituted by one or more substituents selected f~om carboxylic acid amide, cyano, nitro, chlorine, bromine, carbalkoxy and acy-lamido each of 2 to 4 carbon atoms, or alkyl and alkoxy each of 1 to 4 carbon atoms.
Further, we have found that ~-sulfo-propionic acids of the formula C-~ ~ R3-c-c-cH2-so3H Ia 1~ ~ n R
wherein R is a straight-chain, alkyl of 4 ,to 26 carbon atoms, alkenyl of 4 to 26 carbon atoms, a~kylcarbonyl of 4 to 26 carbon atoms, aralkyl of 7 to 26 carbon atoms or 2-ethylhexyl , the individual R~'s may be identical or different and each is hydrogen or alkyl of 1 to 4 carbon atoms, R3 is oxygen or R4 where R4 is -N-hydrogen, alkyl of 1 to 4 carbon atoms or hydroxyethyl, n is 0 or an integer from 1 to 100 and if n is 0, Rl and R3 may also together be H---C C R6 , where R6 is hydroxyethyl or , .
N N
.~, \C/
, R 2 hydrogen and R has the above meanings, may be obtained advanta-geously by reaction of alcohols, acid amides or amines with acid anhydrides if alcohols, acid amides or amines of the formula ; 30 L.
.... ~
1060444 ooæO 30,756 ~ H R ~
Rl ~-C C ~ R3~H II
wher-e Rl, R2, R3 and n have the above meanings, are reacted with ~-sulfocarboxylic acid anhydrides of the formula .~ ~
. O
where R2 ha~ the above meanings~
Further, we have found that an advantageous embodiment of the process is to react the resulting ~-sulfo-propionic acids Ia with alkali, morpholine or a base of the formula . R5 - N IV
where R5 has the above meanin~s, to give ~-sulfo-propionic acid ~ compounds Or the formula 3 ~ H R2\ O R2 ~
1 Rl _ ~ C-C ~ R -C-C2CH2 S 3 y~ Ib 1 in which Rl, R2, R3 and n have the above meaning~ and Y is - ",CH2 CH~ R5 ~ CH2-CH2 , an alkali metal ion or R5-N-H~, where R
the individual R5's may be identical or different and each is an aliphatic radical or hydrogen.
Where sulfo-propionic anhydride, dodecyl alcohol and morpholine . are used, the reaction may be represented by the following equation:
C12H25 OH ~ olc-cH2-cH2-so2 ~~~~ C12H25 o-C-CH2-CH2-S3H
~ H2-C~
+HN ~ O
-3~ /
10609~44 CH C~
Cl2H25-OCO-C~2-CH2-S03 H2N o Compared to the state of the art, the process of the invention gives a large number of new ~-sulfo-propionic acid compounds, in the form of esters, monoacylamides and diacylamides, simply and economically and in good yield and purity.
The starting materials II and III can be reacted in stoichiometric amounts or in excess (of one material), preferably in a ratio of from 0.5 to 2.5 moles of starting material II per mole of starting material III. Preferred starting materials II, III and IV and accordingly preferred products I, Ia and Ib are those wherein R is advantageously straight-chain alkyl of 8 to 24, and especially of 12 to 24, carbon atoms,especially straight-chain alkenyl of 8 to 24, carbon atoms,advantageously straight-chain alkylcarbonyl of 8 to 24, and especially of 12 to 24, carbon atoms, advantageously aralkyl of 10 to 24 and especially of 10 .~ to 18 carbon atoms, in particular nonylphenyl, isooctylphenyl or octylphenyl, or 2-ethylhexyl, the individual R 's may be : 20 identical or different and each is hydrogen or alkyl of 1 to 4 carbon atoms, R is oxygen or R where R is hydrogen, alkyl of . N
1 to 4 carbon atoms or hydPoxyethyl, Z is a hydrogen ion, ,,/CH2-CH~ , . H2N~ ~ O , - .
C~ 2 - C H2 . sodium or potassium or R5 , where the individual R5's may be .' R5-N-H
identical or different and each is advantageously an alkyl of 8 to 24, and especially of 12 to 24, carbon atoms, hydroxyethyl or hydrogen, n is 0 or an integer from 2 to 80, and if n is 0, and R3 may also together be H
. H-C______c_~6 N N -c/
. ~. 4 1060444 oOzO 30,756 where R6 is hydroxyethyl or hydrogen and R2 has the above meaningsO
The above radicals can further be substituted by groups and/or atoms which are inert under the reaction conditions, eOgO
carboxylic acid amide, cyano, nitro, chlorine, bromine, carb-alkoxy and acylamido each of 2 to 4 carbon atoms, or alkyl and alkoxy each of 1 to 4 carbon atomsO It is also possible, and advantageous, to react mixtures of ~traight-chain alcohols, e.g.
those obtained from the oxo ~ynthesis, and further process the resulting mixtureR of products I directly9 eOg~ to give surfactants.
This i~ economically advantageous because it saves isolating the individual alcohols from the mixtures, which in most cases is a laborious operation entailing heavy lossesO A rurther range of very valuable alcohols for the reaction with the sulfocarboxylic acid anhydride is obta;ned by oxyalkylation of straight-chain alcohols with epoxides, e.g. ethylene ox;de and/or propylene oxide, which are reacted with the alcohols in the ratio of rrom 1 to 100 moles Or alkylene oxide or a mixture o~ the epoxides per mole Or alcohol. If mixtures of amines, e~gO fatty amines such as laurylamine, are u~ed as starting materials, mixtures of the sul~onates of these amines with the corresponding ~-sui~opropionic acid amides are obtainedO
Examples of suitable starting materials II are n-butyl , alcohol, 2-ethylhexanol, n-octanol, decanol, dodecanol, tetra-decyl alcohol, octadecyl alcohol, stearic acid ethanolamide, the glycol half-e~ter o~ lauric acid, octylphenol, nonylphenol and dodecylphenol; butylamine, decylamine, dodecylamine, octa-decylamine, dibutylamine, methylbutylamine, methylbenzylamine, methyltetradecylamine and N-ethanol-N-butylamine; n-nonanol, n-undecanol, tridecanol, pentadecanol, hexadecanol, heptadecanol, 3o n-tetracosanol, octadecenyl alcohol 9 2-undecyl-5-hydroxyethyl-imidazoline5 n-nonylamine, oleylamine, 2-ethylhexylamine, hexa-cosanol and lauric acid ethanolamide; the above alcohols oxyalkylated with 2, 3, 4, 5, 25, 80 or 100 moles of ethylene oxide or propylene oxide or moles of ethylene oxide and propylene oxidé (in :: ~5-.
-- ~060444 oOzO 30,756 the ratio Or rrom 0.1 to 20 moles o~ propylene oxide per mole Or ethylene oxide), e~gO nonylphenyl tris oxyethyl alcohol C9H19 ~ ~CH2 CH2 ~ H ; and appropriate mixturesO
Possible starting materials III are ~-sulfopropionic anhydride, ~-sulfopivalic anhydride and the anhydride of 2-ethylhexane-1-sulfonic acid-2-carboxylic acidO
The reaction is a~ a rule carried out at from 0 to 120C, prererably from 20 to 90C, under atmospheric or superatmospheric pressure, continuously or batchwiseO Preferably, no solvent is used. However it iæ also possible to use organic solvents which are inert under the reaction conditions, such as chlorohydro-carbons, e~g. ethylene chloride and chloroform, cyclic ethers, ' e~g. dioxane and tetrahydrofuran, and aliphatic or aromatic hydrocarbons, eOgc toluene, heptane and petroleum etherO
The reaction may, eOgO, be carried out as ~ollows:
the appropriate etarting material II i8 added to the sulfocarb-oxy}ic acid anhydride III, optionally in a solvent, whilst ~tirring well~ The mixture is then kept ror a further 2 to 3 hours at the reaction temperature. The product is isolated by conventional methods, eOgo by distillationO It is, however, more advantageous to neutralize the sulfonic acid Ia which has been .7 formed with bases IV, alkali or morpholine and to isolate the product Ib by conventional methods, eOgO by crystallization ~rom suitable solvents such as alkanols, e.~. ethanol and isobutanol, ~ halohydrocarbons, eOgO ethylene chloride and chloroform, tetra-- ~ hydrofuran, acetone, ethyl acetate and diethyl ether. Where amines : ~
~ II are used, neutralization is conveniently efrected by using an ., :
. ~ -appropriate excess Or amine II. In general, the neutralization is . ~ .
~0 effe¢ted at ~rom 0 to 80C, under atmospheric or superatmospheric ~; pressure, continuously or batchwise, over the course Or ~rom 0.1 to 12 hours, using from 1 to 4, prererably from 106 to 3, equiva-~ lents of base per mole o~ product Ia. Preferred bases are sodium '~ -6-~ .
1060444 oOzO 30,756 and potassium compoundsg especially sodium hydroxide and potassium hydroxide, morpholine9 ammonia, pr;mary, secondary or tertiary alkylamines of 1 to 26, advanta~eously of 1 to 4 or 8 to 24, carbon atoms per alkyl group, eOgO dimethylamine, methylamine, trimethylamine, triethylamine, diethylamine, mono-ethylamine, propylamine, dipropylam;ne, tripropylamine, dibutyl-amine, butylamine, tr;butylamine, nonylamine, dinonylamine, tri-nonylamine, tetracosylamine, isopropylamine, diisopropylamine, triisopropylamine, stearyIamine, distearylamine and tristearyl-amine, and amine~ containing hydroxyethyl groups, eOgO ethanolamine,diethanolamine, triethanolamine, butyldiethanolamine and dimethyl-ethanolamineO After neutralization, the salt ;s isolated by con ~entional methods, eOgO by filtrationO
The new products I which can be manufactured by the process Or the invention are text;le assistants, eOgO washing, cleansing or wetting agents, dishwashing detergents, hair shampoos, emulsi-~iers, ~lotation agents, plasticizers and ~aluable starting materials ror the manufacture of such a~sistants, as well as ror the manufacture of dyes and pesticidesO Thus, with all products of the examples which ~ollow, eOgO with a mixture Or sodium ,' (dodecyl-dioxyethyl propionate)-B-sulfonate and sodium (tetra-decyl-dioxyethyl propionate)-B-sulfonate (in the ratio Or ~
a very good wetting erfect on cellulos;c material and a very good ~ detergent action when laundering cotton fabrics and washing J~ woolen article~, impregnated with oli~e oil or ~ineral oil, i8 achieved at concentrations o~ only from 10 to.100 parts per 1,000 parts o~ water~ Furthermore, all the products Or the examples which follow, eOgO the mixture of sodium (dodecyl-tris-oxyethyl propionate)-~-sulfonate and ~odium (octadecyl-tri~-oxyethyl propio-nate)-R-sulfonate tin the ratio of 1 : 1) can be used in dish-washing detergents of moderate foaming power, having, eOg., the following composition:
5 parts o~ diethanQlamine alkylbenzenesulfonate ~06~444 O.Z0 30,756 5 parts of nonylphenol condensed with 10 moles of ethylene oxide 5 parts of ~odium (dodecyl/octadecyl-tris-oxyethyl propionate)-~-sulfonate (1 : 1) 5 parts Or isopropanol 5 parts of tetrapotassium pyropho~phate 75 parts of water In the Examples which follow, parts are by weight.
29.6 parts Or n-butanol are added to a melt o~ 5405 parts o~ ~-sulropropionic anhydride at 65C, whilst stirring~ A~ter stirring ror a rurther two hours at 70C, the sulfonic acid I
which i6 formed is neutralized by adding 51.7 parts Or butyl-diethanolamine. 122 parts (8~.8% Or theory) of butyldiethanol-, ammonium ~butyl propionate)-~-~ulfonate are obtained as a brown ; oil. n20 ~ 1.47120 ~ 130 parts o~ 2-ethylhexanol are added ~lowly to a melt of `! 163 parts o~ ~-sul~opropionic anhydride at 75C A~ter stirring for a further three hours at 80C, the mixture i~ adjusted to pH
~ 5 with 90 parts Or 50 per cent strength by weight sodium hydroxide ¦ ~olution at 50C, whilst ~tirring. Sodium (2-ethylhexyl propionate)-A-sulronate is obtained in the rorm of a 64 per cent strength by weight paste which is readily water-soluble. Yield: 265 parts (9005% of theory)0 n20 - 1.4589.
(a) 130 parts Or dodecyl alcohol are added slowly to a melt Or 95 parts of ~-sulPopropionic anhydride at from 75 to 80C, whilst ¦; stirring and slightly cooling the mixture. A~ter stirring ror a ¦ 3 further three hours at 85C~ 225 parts of (dodecyl propionate)-~-sulronic acid Or melting point 36 - 38C (arter recry~tallization rom ethylene chloride) are obtained.
:
106~444 o ~z o 30,756 (b) 28.6 parts of morpholine are added to 9608 parts of the sul~onic acid I at 40C, whilst stirringO The mixture is diluted with 100 parts of ethylene chloride and stirred for 2 hours at 60C. After adding 800 parts of petroleum ether, the morpholinium (dodecyl-propionate)-~-sulfonate which has crystallized out is rilt;ered of~ and recrystallized from ethanolO Melting point 74 -77C; yield: 100 parts (81~5% of theory)0 65.5 parts of ~-sulfopivalic anhydride are introduced into 74.5 parts of dodecyl alcohol at 25C, whil~t stirring. When the - exothermic reaction ha~ ended, the mixture is slowly warmed to 70C and stirred at this temperature for 3 hours~ The (dodecyl pivalate)-~-sulfonic acid is ob~ained in the form of a yellow ; oil Or n20 = lo 45630 37 parts of morpholine are added slowly to the product Io Arter dilution with 250 part~ o~ petroleum ether, the mixture i8 stirred ~or one hourO ~he ~uspension obtained is cooled and the product is then filtered Or~ and re¢rystallized ~rom acetoneO
Melting point 7005 ~ 72C; yield-146 parts (74o2%-0~ theory) 20 Or morpholinium (dodecyl pivalate)~ ulfonate.
,~ 48D5 parts of a mixture o~ straight-chain alcohols, con-l taining 2705% by weight Or nonyl alcohol, 12% by weight o~ decyl !
alcohol and 6005% of undecyl alcohol are added to a melt o~ 41 parts of ~-sulfopropioni~ anhydride at 65C, whilst stirring.
~ ~:
ll~ After stirring for a further three hours at 70C, the mixture is ~ .:,pr, cooled and neutralized-with 48 parts o~ 25 per cent strength by weight sodium hydroxide solution at 30QC. A water-soluble paste '~ containing 137 parts (100% o~ theory) of sodium (nonyi, decyl and 30 undecyl propionate)-~-sulfonate of melting point 280 - 285C
i (with decomposition) (after recrystallization rrom acetone) is obtainedO The ratio of the esters corresponds to the ratio Or the alcohols used.
'~
1060444 o zO 30,756 64 parts o~ a mixture of straight-chain alcohols con-taining 2805% by weight of dodecanol, 27% by weight of tri-decanol, 23% by weight of tetradecanol and 210 5% b~ wei~ht of pentadecanol are added to a melt of 41 parts of sulfopropionic anhydride at ~rom 70 to 80C After stirring for a further three hours at 70C, the sulfonic.acid.I, which is in.the ~orm of a dark brown oil, is neutralized by adding 2605 parts Or 50 per cent strength by weight sodium hydroxide solution.
130 parts (100% of theory) o~ ~odium.(tridecyl, dodecyl, tetradecyl and pentadecyl propionate)-~-sulfonate o~ nD =
1 4613 are obtained. The ratio of the esters corresponds to the ratio of the alcohols usedO
78 parts Or a mixture of n-hexadecyl alcohol and n-octadecyl alcohol (2: 1) are added to a melt of 41 parts Or ~-sul~opropionic anhydride, whilst stirring~ Arter ~tirring ~or a further three hours at 75C, the brown melt is.taken up in 350 parts of ethylene chloride and 29 parts o~ morpholine 20 are added whilst stirring at from 50 to 70~0 The ethylene ¢hloride is distilled off under. reduced.pressure .and the re~i-due i8 recrystallized ~rom ethanolO 142 parts (96% Or theory) o~ morpholinium (hexadecyl/octadecyl propionate)~-sulronate are obtained in the form o~ light brown: crystals. rlelting point 76 ~ 80Co The ratio of the esters corresponds to the ratio o~ the alcohols used.
68.5 parts o~ a fatty alcohol mixture containing 41%
by weight of dodecanol, 30% by weight of tetradecanol, 18% by 30 weight of hexadecanol and 11% by weight Or octadecanol are added to a melt of 41 parts of sulfopropionic anhydride at from 60 to 70C J whilst stirring After stirring ror a further three hours, the sulfonic acid T iS obtained as a O.Z0 30,756 brown oil which is neutralized by adding 26~4 part~ o~ 50 per cent strength by weight sodium hydroxide solution at 30C~
Precipitation with acetone gives 93 parts of sodium (dodecyl, tetradecyl, hexadecyl and octadecyl/propionate)-~-sulfonate) a~ white cry~tals which give a clear solution in waterO Melting point ~00C (with decomposition)0 The ratio of the esters corres-pond~ to the ratio o~ the alcohol~ used.
99.5 parts o~ a mixture,of n-dodecyl alcohol and n-tetra-decyl alcohol (55.5 : 4505) oxyethylated with 3 mole~ of ethylene oxide are added to a melt of 41 parts of R-~ulfo-propionic anhy-dride at from 50 to 70C~ whilst stirring. A~ter stirring for a ~ùrther three hours at 70C, 2806 parts,or morpholine are added to the mixture at ~rom 40 to 70C and the batch i8 stirred for a ~urther ~ hours. 159 part~ (94% o~ theory) Or morpholinlum ~do~ecyl/tetradecyl-tri~-oxyethyl propionate)-~-sulronabe are obtiined as a light brown pasteO n20 - 1.4598~.The.lratio o~ the e~torB ¢orre~pond~ to the ratio Or the.alcohols used.
6~.5 parts o~ ~-sul~opi~alic anhydride,are introduced.in~o 133 parts of a mixture o~ n-dodecyl-..and n~tetradecyl-tris-oxyethyl alcohol (55 ; 45) at from 60 to 70C. 198 parts (a practically quantitative yield) o~ the ~ulfonic acid-I are obtained:as a red-brown oil-o~ nD = 1.4613.
The mixture i3 neutralized by adding ~9.5 parts Or 50 per .
cent strength by weight sodium hydroxide solution. 237 parts ~, (a practically.quantitative yield) of sodium,(dodecyl/tetradecyl-tris-oxyethyl pivalate)-~-sulfonate are obtained,as a 91.6 per cent strength.a~ueous solution. The ratio.of the e~ters corresponds ~0 to the ratio of the alcohols u~ed.
9.5 parts o~ sulfopropionic anhydri~e are-added to 227-parts o~ a mixture.o~ straight-chain alcohol~, containin~.65% by weight ,.~
~C~60444 OOZo 30,756 of hexadecanol and 35% by weight of octadecanol, which has been oxyethylated with 80 moles o~ ethylene oxide. After stirring for a rurther three hours at rrom 75 to 80C, the (propionic acid e~ter)-sulronic acids I are obtained as a brown oil (n50 _ 1.4617).
Thi~ is neutralized by adding 236 parts of water and 10 parts o~
50 per cent strength by weight sodium hydroxide solution at from 30 to 40C. 482 parts of the sodium (propionic acid ester)-~-sulronate based on the above alcohol mixture are obtained as an aqueous paste. The ratio of the esters corresponds to the ratio Or the alcohols used.
, EXAMPLE 12 378 part~ Or n-nonanol which has been oxyalkylated with moles Or ethylene oxide and 2 moles Or propylene oxide are added to a melt of 129 parts of ~-sul~opropionic anhydride at from 70 to 80C, whilst stirring. Arter stirring for a further two hours at 80~, 508 parts (a practically quantitative yield) o~ (nonylpentaoxyethyl propionate)-~-sulfonic acid,are obtained ~ as a brown oil (n30 = 104590)o The product i8 nçutralized by ', adding 57 parts of 50 per cent strength by weight sodium hydroxide ~olution and 250 parts of water, 815 parts (a practically quanti-I tative yield) of the sodium salt are obtained in the form o~ a 1 66 per cent strength aqueous solutionO
j EXAMPLE 13 i ~ 106 parts of n tetracosanol are added to a melt Or 41 parts ~-sulfopropionic anhydride at from 60 to 70C,,whilst stirring.
1 A~ter stirring for a further four hours at 70C, 147 parts (a ¦~ practically quantitative yield) of (tetracosyl propionate)-~-f sul~oni,c acid are obtained as a brown oil (n50~= 104537). Arter ;~ dilution with 260 parts of water, the mixture is neutralized with 24 parts o~ 50 per cent strength by weight sodium hydroxide soiution.
430 parts (a practically quanti~ative yield) or the sodium salt are obtained in the rorm Or a 35 per cent strength aqueous oil.
`:
OOZo 30,756 78 parts Or n-octadecenyl alcohol are added to 41 parts Or sulfopropionic anhydride at 60C, whilst stirring~, Arter ~tirring ror a further three hours at 70C, 119 parts (a prac-tically quantitative yield) of (octadecenyl propionate)-~-~ulfonic acid are obtained as a brown oil (nD = 1.4550). 45 parts Or triethanolamine are added at 70Co The mixture is stirred for a further 2 hours at 70C, 163 parts (a practically quantitative yield) Or pasty triethanolamine salt are obtained.
1180 5 parts of nonylphenol which has been oxyalkylated with 4 moles Or ethylene oxide are added to 41:parts of,~-sulropro-pionic anhydride at 70C, whilst stirring. After stirring for a rurther two hours at 75C, 4208 parts Or dibutylamine, are added at ~rom 40 to 60C and the mixture is stirred ror a rurther 2 hour~ at 70C. 192 part~ (97% o~ theory) Or dibutylan~onium ~nonylphenyl-tetraoxyethyl propionat:e)-~-~ulronate.are: obtained , a~ a brown oil (n20 - 1.4904).
~,, EXANPI,E 16 13.6 parts of~ ~-sulfopro.pionic anhydride .are added at 70C, ~, whilst stirring, to 130.6 parts of .-isooctylphenol which ba~ been oxyalkylated with 25 moles Or ethylene oxideO Arter 3.hours at 70C, 144 D2 parts (a practically quantibative yield) of product .' I (n20 ~ 1.4847) are obtained" A~ter adding.2.70 parts o~ water, 12 parts Or 50 per cent strength by weight sodium hydroxide solution , are introduced and the mixture is stirred for 2 hours at 40~.;, 426 parts (a practically quantitative yield) o~ sodium (isooctyl-'~ phenyl propionate)~ ul~onate:are obtained as. a light brown 35 per cent strength aqueous oil.
;- i34 parts Or 2-undecyl-5-hydroxyethyl-imidazoline are added , to 68 part~ o~ ~-sulropropionic.anhydride at 80~ he mixture is stirred ror a further 4 hours at 80C, givin~;.l98.part~ (98% Or `- ~060444 0OZo 309756 theory) of N-(2-undecyl-5-hydroxyethyl~imidazolinyl)-propionic acid-R-sulfonic acidO
54O5 parts of ~ulfopropionic anhydride are added to a solution Or 120 part~ of n-nonylamine in 250 parts Or ethylene chloride at 40C, whil~t stirringO After stirring for a further two hours at 45C, the suspension is riltered and the crystalline product is recrystallized from ethylene-chlorideO 86 parts ' (71.4% of theory) of nonylammonium (propionyl-nonylamide)-~-sulfonate are obtained as colorless crystals of melting point / 167 ~ 169Co :, EXAMPLE 19 41 parts of sulfopropionic anhydride are added to a solution :, of 160 parts Or oleylamine in 200,parts Or ethylene,chloride at from 50 to 60C. Arter one hour, 25 parts Or 50,per cent strength ,~ by weight ~odium hydroxide so}ution are added to the red-brown ,~ oil obtained, and the mixture is stirred for,one hour at 80C.
A~ter cooling, the suspension is riltered and the,re~idue is heated with acetone at 56C,ror halr an hourO 167 parts (650~%
.~ 20 of theory) of sodium (propionyl-oleylamide)-~-sulfonate Or melting point 304 - 309C are obtainedO
3~ 144 parts o~ di-(2-ethylhexyl)-,amine are added to 41 parts Or sulfopropionic anhydride at-70 - B0C, whilst ~tirringO After ~: stirring for a further two hour~ at 130C, 176,parts (70% Or : '~
: ~ theory) Or di-(2-ethylhexyl)-ammoniwn (propionyl-di-(2-ethylhexyl)-, ~ amide)-~-sulfonate are obtained as a brown. oil of nD s 1.4724.
~, 243 parts of lauric acid ethanolamide are added to 136 parts 30 of ~-sulfopropionic anhydride at from 70 to 80C, whilst stirring.
After stirring for a furkher three hours at 80C, 379 parts (practically the quantitative yield) Or (propionyl-lauroylethanol-amide)~ ulfonic acid of n50 = 1.4719 are obtained.
106044~ oOz. 30,756 After dilution with 250 parts of water, the mixture is neutralized with 120 parts of 50 per cent strength by weight sodium hydroxide solution. 743 parts (a practically quantitative yield) of the sodium salt are obtained in the form of a 55 per cent strength white paste.
~15-
Claims (9)
1. .beta.-sulfo-propionic acid compounds of the formula where R1 is a straight-chain, alkyl of 4 to 26 carbon atoms, alkenyl of 4 to 26 carbon atoms, alkylcarbonyl of 4 to 26 carbon atoms, aralkyl of 7 to 26 carbon atoms, or 2-ethylhexyl, the individual R2's may be identical or different and each is hydrogen or alkyl of 1 to 4 carbon atoms, R3 is oxygen or R4 where R4 is hydrogen, ' -N-alkyl of 1 to 4 carbon atoms or hydroxyethyl, Z is a hydrogen ion, an alkali metal ion or , the individual R5's being identical or different and each being an alkyl of 1 to 26 carbon atoms, hydroxyethyl or hydrogen, n is O or an integer from 1 to 100, and if n is O,R1 and R3 may also together be R6 being hydroxyethyl or hydrogen and R2 having the meanings given above, and the above radicals being optionally further be substituted by one or more substituents selected from carboxylic acid amide, cyano, nitro, chlorine, bromine, carbalkoxy and acylamido each of 2 to 4 carbon atoms, or alkyl and alkoxy each of 1 to 4 carbon atoms.
2. A process for the manufacture of a .beta.-sulfo-propionic acid of the formula Ia where R is a straight-chain aliphatic radical of at least 4 carbon atoms, an araliphatic radical, or 2-ethyl-hexyl, the individual R2's are identical or different and each is hydrogen or an aliphatic radical, R3 is oxygen or R4, R4 being hydrogen or an aliphatic ' -N-radical, n is O or an integer from 1 to 100 and if n is O,R1 and R3 may also together be.
R6 being hydroxyethyl or hydrogen and R2 having the meanings given above, by reaction of an alcohol, acid amide or amine with an acid anhydride, wherein an alcohol, acid amide or amine of the formula II
where R1, R2, R3 and n have the meanings given in claim 1 is reacted with a .beta.-sulfocarboxylic acid anhydride of the formula III
where R2 has the above meanings.
R6 being hydroxyethyl or hydrogen and R2 having the meanings given above, by reaction of an alcohol, acid amide or amine with an acid anhydride, wherein an alcohol, acid amide or amine of the formula II
where R1, R2, R3 and n have the meanings given in claim 1 is reacted with a .beta.-sulfocarboxylic acid anhydride of the formula III
where R2 has the above meanings.
3. A process as claimed in claim 2, wherein the resulting .beta.-sulfo-propionic acid Ia is reacted with a base selected from alkali, morpholine and basesof the formula IV
where R5 has the meanings given in claim 1, to give a .beta.-sulfo-propionic acid compound of the formula Ib in which R1, R2, R3 and n have the meanings given in claim l and Y is , an alkali metal ion or the individual R5's being identical or different and each being an aliphatic radical or hydrogen.
where R5 has the meanings given in claim 1, to give a .beta.-sulfo-propionic acid compound of the formula Ib in which R1, R2, R3 and n have the meanings given in claim l and Y is , an alkali metal ion or the individual R5's being identical or different and each being an aliphatic radical or hydrogen.
4. A process as claimed in claim 2, wherein the reaction between starting materials II and III is carried out using from 0.5 to 2.5 moles of starting material II per mole of starting material III.
5. A process as claimed in claim 2, wherein the reaction between starting materials II and III is carried out at from 0 to 120°C.
6. A process as claimed in claim 2, wherein the reaction between starting materials II and III is carried out at from 20 to 90°C.
7. .beta.-sulfo-propionic acid compounds of the formula where R1 is straight-chain alkyl of 8 to 24 carbon atoms, straight-chain alkenyl of 8 to 24 carbon atoms, straight-chain alkylcarbonyl of 8 to 24 carbon atoms, aralkyl of 10 to 24 carbon atoms or 2-ethylhexyl, the individual R2's are identical or different and each is hydrogen or alkyl of 1 to 4 carbon atoms, R3 is oxygen or R4 , R4 being hydrogen,alkyl of 1 to 4 carbon atoms or hydroxy-' -N-ethyl, Z is a hydrogen ion, a sodium or potassium ion or , the individual R5's being identical or different and each being alkyl of 8 to 24 carbon atoms, hydroxyethyl or hydrogen, n is O or an integer from 2 to 80 and if n is O,R1 and R3 may also together be R6 being hydroxyethyl or hydrogen and R2 having the meanings given above, and the above radicals being optionally further substituted by one substituent selected from carboxylic acid amide, cyano, nitro, chlorine, bromine, carbalkoxy and acylamido each of 2 to 4 carbon atoms or alkyl and alkoxy each of 1 to 4 carbon atoms.
8. A process as claimed in claim 2, wherein the reaction is carried out with n-butyl alcohol, 2-ethyl-hexanol, n-octanol, decanol, dodecanol, tetradecyl alcohol, octadecyl alcohol, stearic acid ethanolamide, the glycol half-ester of lauric acid, octyl-phenol, nonylphenol, dodecylphenol, butylamine, decylamine, dode-cylamine, octadecylamine, dibutylamine, methylbutylamine, methyl-benzylamine, methyltetradecylamine, N-ethanol-N-butylamine, n-nonanol, n-undecanol, n-tridecanol, n-pentadecanol, n-hexadecanol, n-heptadecanol, n-tetracosanol, octadecenyl alcohol, 2-undecyl-5-hydroxyethyl-imidazoline, n-nonylamine, oleylamine, 2-ethylhexyl-amine, hexacosanol or lauric acid ethanolamide, or any of the above alcohols oxyalkylated with 2, 3, 4, 5, 25, 80 or 100 moles of ethylene oxide or propylene oxide or moles of a mixture of ethylene oxide and propylene oxide (in the ratio of from 0.1 to 20 moles of propylene oxide per mole of ethylene oxide), nonyl-phenyl-tris-oxyethyl alcohol , a mixture of two or more of those compounds, as the starting material II, and with .beta.-sulfo-propionic anhydride, .beta.-sulfopivalic anhydride or the anhydride of 2-ethylhexane-1-sulfonic acid -2-carboxylic acid as the starting material III.
9. A process as claimed in claim 3, wherein the reaction of the .beta.-sulfo-propionic acid Ia is carried out at from 0 to 80°C using from 1 to 4 equivalents of base per mole of product Ia, the base being selected from sodium hydroxide, potassium hydroxide, morpholine, ammonia, dimethylamine, methylamine, trimethylamine, triethylamine, diethylamine, monoethylamine, propylamine, dipropylamine, tripropylamine, dibutylamine, butylamine, tributylamine, nonylamine, dinonylamine, trinonylamine, tetracosylamine, isopropylamine, diisopropylamine, triisopropyla-mine, stearylamine, distearylamine, tristearylamine, ethanolamine, diethanolamine, triethanolamine, butyldiethanolamine and dimethylethanolamine.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19742440209 DE2440209A1 (en) | 1974-08-22 | 1974-08-22 | BETA-SULFO-PROPIONIC ACID COMPOUNDS AND THE PROCESS FOR THEIR PRODUCTION |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1060444A true CA1060444A (en) | 1979-08-14 |
Family
ID=5923781
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA233,420A Expired CA1060444A (en) | 1974-08-22 | 1975-08-13 | .beta.-SULFO-PROPIONIC ACID COMPOUNDS AND PROCESS |
Country Status (9)
| Country | Link |
|---|---|
| JP (1) | JPS51125022A (en) |
| AT (1) | AT342559B (en) |
| BE (1) | BE832650A (en) |
| CA (1) | CA1060444A (en) |
| CH (2) | CH616407A5 (en) |
| DE (1) | DE2440209A1 (en) |
| FR (1) | FR2282425A1 (en) |
| GB (1) | GB1509230A (en) |
| IT (1) | IT1039297B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB0407908D0 (en) | 2004-04-07 | 2004-05-12 | Univ York | Ionic liquids |
| CN113694823B (en) * | 2021-02-25 | 2022-04-22 | 山东大学 | Secondary amide sulfonic acid surfactant, and preparation method and application thereof |
-
1974
- 1974-08-22 DE DE19742440209 patent/DE2440209A1/en not_active Withdrawn
-
1975
- 1975-07-16 IT IT2547475A patent/IT1039297B/en active
- 1975-08-13 CA CA233,420A patent/CA1060444A/en not_active Expired
- 1975-08-20 CH CH1084075A patent/CH616407A5/en not_active IP Right Cessation
- 1975-08-21 GB GB3474875A patent/GB1509230A/en not_active Expired
- 1975-08-21 AT AT649075A patent/AT342559B/en not_active IP Right Cessation
- 1975-08-21 FR FR7525853A patent/FR2282425A1/en active Granted
- 1975-08-22 JP JP50101304A patent/JPS51125022A/en active Pending
- 1975-08-22 BE BE159380A patent/BE832650A/en unknown
-
1979
- 1979-09-27 CH CH868679A patent/CH618160A5/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| FR2282425A1 (en) | 1976-03-19 |
| IT1039297B (en) | 1979-12-10 |
| GB1509230A (en) | 1978-05-04 |
| AT342559B (en) | 1978-04-10 |
| BE832650A (en) | 1976-02-23 |
| FR2282425B3 (en) | 1978-04-07 |
| CH618160A5 (en) | 1980-07-15 |
| DE2440209A1 (en) | 1976-03-04 |
| CH616407A5 (en) | 1980-03-31 |
| JPS51125022A (en) | 1976-11-01 |
| ATA649075A (en) | 1977-08-15 |
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