WO2013123633A1 - Process for producing a sulfate salt of alkyl glyceryl ether - Google Patents
Process for producing a sulfate salt of alkyl glyceryl ether Download PDFInfo
- Publication number
- WO2013123633A1 WO2013123633A1 PCT/CN2012/071335 CN2012071335W WO2013123633A1 WO 2013123633 A1 WO2013123633 A1 WO 2013123633A1 CN 2012071335 W CN2012071335 W CN 2012071335W WO 2013123633 A1 WO2013123633 A1 WO 2013123633A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- alkyl
- process according
- sulfate
- glyceryl ether
- gas
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/24—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of esters of sulfuric acids
Definitions
- the present invention relates to a process for producing a sulfate salt of alkyl glyceryl ether. Specifically, the present invention relates to a process for producing a sulfate salt of alkyl glyceryl ether starting from alkyl glycidyl ether. Background
- the detergent industry has been increasing its usage of anionic surfactants, particularly the biodegradable aliphatic and/or alicyclic ether sulfate and sulfonate salts.
- the sulfate salts of alkyl glyceryl ethers are useful as biodegradable surfactants in detergent compositions. They can notably be used as surface active reagent in homecare, personal care and other industrial zone as detergent, foamer or emulsifier.
- the sulfate salts are usually prepared by reaction of the hydroxyl group with a sulfating agent and neutralization of the sulfate product with base.
- a sulfating agent for example, US4217296A discloses a process for preparing a mixture of sulfate salts of Cio-20 linear alkyl glyceryl ether alcohols by reacting a stoichiometric excess of &.20 linear alkyl alcohol with glycidol predissolved in hexyl acetate to selectively produce Cio-20 linear alkyl glyceryl ether alcohols containing 1-3 glyceryl units, sulfating said ether alcohols, and neutralizing the sulfates with base.
- alkyl glyceryl ether alcohols it is known that certain of such compounds may be prepared by reacting the corresponding aliphatic alcohol and glycidol.
- an alkali is used as catalyst which tends to have some problems such as low conversion of the alcohol and large impurity for removal of unreacted alcohol.
- working with glycidol has the drawback that the production of glycidol is difficult and expensive and that it is difficult to prevent the glycidol from self-polymerizing.
- WO 03104199A2 discloses a process for producing an organic catalyst comprising preparing a cyclic sulfate of monoalkyl glyceryl ether from alkyl glycidyl ether and SO3/D F as reactant in the presence of high toxic toluene as solvent and then reacting the cyclic sulfate with dihydroisoquinoline to form an organic catalyst comprising iminium or oxaziridinium moieties.
- This reference is silent to the production of the sulfate salt of monoalkyl glyceryl ether.
- the objective of the present invention is to provide a process for preparing a sulfate salt of alkyl glyceryl ether, which is environmental friendly, simple and has a high yield.
- the present invention provides a process for preparing a sulfate salt of alkyl glyceryl ether, comprising:
- alkyl glycidyl ethers used as reactants are commercially available materials and it does not need to convert alkyl glycidyl ethers to alkyl glyceryl ethers.
- alkyl glyceryl ether sulfates can be made directly from alkyl glycidyl ethers and S03 gas with a high selectivity and high yield.
- the present process is a simple two steps process for producing alkyl glyceryl ether sulfate salt: the first step is preparing a cyclic sulfate of alkyl glyceryl ether by reacting alkyl glycidyl ether and S03 gas; and the second step is directly neutralizing the cyclic sulfate of alkyl glyceryl ether in the reaction system to sulfate salts of alkyl glyceryl ether.
- the separation of the intermediate alkyl cyclic glycidyl ether is not needed.
- S03 is used in the form of gas and therefore no complex thereof, for example, S03/DMF or S03/pyridme will be involved in the reaction system.
- S03/DMF or S03/pyridme will be involved in the reaction system.
- the present inventors have surprisingly found that a highly-selective reaction can be realized by reacting alkyl glycidyl ether and S0 3 gas and, after hydrolysis by alkaline solution, a high purity monoalkyl glyceryl ether sulfate salt can be successfully obtained.
- the sulfate salt of alkyl glyceryl ether produced by the present invention has high water solubility and is excellent in foaming power, resistance to hard water, an ability to disperse scum. Moreover, it has low stimulation to the skin and excellent biodegradability and can be used as cleaning components excellent in cleaning and foaming abilities even at low temperatures.
- reaction scheme When S03 gas is used as the gas containing SO 3 and a NaOH solution is used for hydrolyzing, the reaction scheme may be as shown below:
- the present invention provides a process for preparing a sulfate salt of alkyl glyceryl ether, comprising:
- the process according to the present invention is very simple and easy to be operated. Since the alkyl cyclic glycerol sulfate obtained in step a) can be directly reacted with an alkaline solution to produce the sulfate salt of alkyl glyceryl ether with a high purity, the separation of the intermediate alkyl cyclic glycerol sulfate from the reaction system in step a) can be omitted. Moreover, in the process according to the present invention, S03 gas is used in the form of pure gas or a gas mixture and therefore no impurity, for example, dimethyl formamide (DMF), pyridine or SO 3 /DMF complex or SO 3 Pyridine complex, will be incorporated in the reaction medium.
- DMF dimethyl formamide
- pyridine pyridine
- SO 3 /DMF complex SO 3 Pyridine complex
- the above step a) is carried out under a temperature in a range of from about 10 to about 90°C.
- alkyl glycidyl ethers may be used as starting materials, as for example a mixture of at least two different glycidyl ethers.
- the alkyl glyceryl ether is a compound of formula (I) or (II) :
- R is an alkyl
- n is comprised between 0 and 10
- alkyl means a linear or branched alkyl group optionally substituted with one or more substituent selected from the group consisting of lower alkyl, lower alkoxy, lower alkylsulfanyl, lower alkylsulfenyl, lower alkylsulfonyl, oxo, hydroxy, mercapto, amino optionally substituted by alkyl, carboxy, carbamoyl optionally substituted by alkyl, aminosulfonyl optionally substituted by alkyl, nitro, cyano, halogen, or lower perfluoroalkyl, multiple degrees of substitution being allowed.
- alkyl examples include, but are not limited to, n-butyl, n-pentyl, isobutyl, isopropyl, and the like.
- lower means that the alkyl moiety of a group has 1 to 30, preferably 10 to 20, still more preferably 12 to 16 carbon atoms.
- the alkyl used in the present invention comprises 1-40, preferably 5-30, more preferably 10-16 carbon atoms.
- R is preferably an alkyl comprising from 1 to 40 carbon atoms.
- R may be a linear or branched alkyl group optionally substituted with one or more substituent.
- the sulfate salt of alkyl glyceryl ether is referably a compound of formula ( ⁇ ) :
- R is an alkyl
- n is comprised between 0 and 10 X is H or S03M
- Rl is OS03M, OH, or an alkoxy group
- R2 is OSO3M, OH, or an alkoxy group
- M is an alkaline earth metal
- Rl and/or R2 are preferably an alkoxy group chosen from methoxyl, ethoxyl and propoxyl.
- the gas containing S0 3 comprises at least 5% by volume of SO 3 gas.
- the gas use din this step can notably be a S03 gas.
- the gas containing SO 3 may also be a mixture of SO 3 gas and an other gas, notably an inert gas.
- the inert gas is preferably selected from the group consisting of dry air, N 2 or mixtures thereof.
- the molar ratio of alkyl glycidyl ether / SO 3 may be comprised between 1.0:0.2 to 1.0:2.0.
- said alkaline solution is a solution of at least one selected from the group consisting of sodium hydroxide (NaOH), potassium hydroxide (KOH), sodium carbonate (Na2CO3), sodium bicarbonate (NaHCO3), sodium sulfite ( a2SO), sodium bisulfite (NaHS03), potassium carbonate (K2C03), potassium bicarbonate (KHCO3), potassium sulfite (K2SO3), potassium bisulfite (KHS03), ammonia, ammonium hydroxide, MeONa, EtONa or mixtures thereof. More preferably, said alkaline solution is an aqueous solution of NaOH.
- This reaction is preferably run at a temperature comprised between 30-150 °C with an alkaline solution in solvent; such as water, methanol, ethanol, propanol, butanol, acetonitrile, actone, dimethyl sulfoxide, dimethylformamide, tetrahydrofuran, diethylether, chloroform, glycol, ethylene glycol dimethyl ether, dioxane or mixture of them.
- solvent such as water, methanol, ethanol, propanol, butanol, acetonitrile, actone, dimethyl sulfoxide, dimethylformamide, tetrahydrofuran, diethylether, chloroform, glycol, ethylene glycol dimethyl ether, dioxane or mixture of them.
- the chemical shifts for monoalkyi glycerol ether sulfates are: 0.8-4.5ppm.
- a 100ml three necked round-bottom flask was equipped with a cooling system and a gas inlet.
- 0.1 mol alkyl (Ci 2 ) glycidyl ether was added to the flask, and reacted with 0.103mol of sulfur trioxide at a temperature of 80°C.
- the sulfur trioxide was driven off by heating from a corresponding quantity of 65% by weight oleum, diluted with nitrogen to a concentration of 5% by volume.
- the sulfur trioxide was introduced to the mixture of alkyl glycidyl ether over 30mins.
- the crude sulfatization product alkyl cyclic glycerol sulfate (ACGS) was obtained.
- a 100ml three necked round-bottom flask was equipped with a cooling system and a gas inlet.
- 0.1 mol alkyl (C 12 .i 4 ) glycidyl ether was added to the flask, and reacted with 0.103mol of sulfur trioxide at a temperature of 80 ° C .
- the sulfur trioxide was driven off by heating from a corresponding quantity of 65% by weight oleum, diluted with nitrogen to a concentration of 5% by volume.
- the sulfur trioxide was introduced to the mixture of alkyl glycidyl ether over 30mins.
- the crude sulfatization product alkyl cyclic glycerol sulfate (ACGS) was obtained.
- a 100ml three necked round-bottom flask was equipped with a cooling system and a gas inlet.
- 0.1 mol alkyl (Cg) glycidyl ether was added to the flask, and reacted with 0.103mol of sulfur trioxide at a temperature of 80C .
- the sulfur trioxide was driven off by heating from a corresponding quantity of 65% by weight oleum, diluted with nitrogen to a concentration of 5% by volume.
- the sulfur trioxide was introduced to the mixture of alkyl glycidyl ether over 30mins.
- the crude sulfatization product alkyl cyclic glycerol sulfate (ACGS) was obtained.
- a 100ml three necked round-bottom flask was equipped with a cooling system and a gas inlet.
- 0.1 mol alkyl (C ]2 ) glycidyl ether was added to the flask, and reacted with 0.103mol of sulfur trioxide at a temperature of 80 °C .
- the sulfur trioxide was driven off by heating from a corresponding quantity of 65% by weight oleum, diluted with nitrogen to a concentration of 5% by volume.
- the sulfur trioxide was introduced to the mixture of alkyl glycidyl ether over 30mins.
- the crude sulfatization product alkyl cyclic glycerol sulfate (ACGS) was obtained.
- a 100ml three necked round-bottom flask was equipped with a cooling system and a gas inlet.
- 0.1 mol 2-((2-(dodecyloxy)ethoxy)methyl)oxirane was added to the flask, and reacted with 0.103mol of sulfur trioxide at a temperature of 80 ° C .
- the sulfur trioxide was driven off by heating from a corresponding quantity of 65% by weight oleum, diluted with nitrogen to a concentration of 5% by volume.
- the sulfur trioxide was introduced to the mixture of 2-((2-(dodecyloxy)ethoxy)methyl)oxirane over 30mins.
Abstract
The present invention relates to a process for producing a sulfate salt of alkyl glyceryl ether, comprising: a) reacting an alkyl glycidyl ether with a gas containing S03 to produce an alkyl cyclic glycerol sulfate; and b) hydrolyzing the alkyl cyclic glycerol sulfate with an alkaline solution to produce the sulfate salt of alkyl glyceryl ether.
Description
PROCESS FOR PRODUCING A SULFATE SALT OF ALKYL
GLYCERYL ETHER
Technical Field
The present invention relates to a process for producing a sulfate salt of alkyl glyceryl ether. Specifically, the present invention relates to a process for producing a sulfate salt of alkyl glyceryl ether starting from alkyl glycidyl ether. Background
In recent years, the detergent industry has been increasing its usage of anionic surfactants, particularly the biodegradable aliphatic and/or alicyclic ether sulfate and sulfonate salts. The sulfate salts of alkyl glyceryl ethers are useful as biodegradable surfactants in detergent compositions. They can notably be used as surface active reagent in homecare, personal care and other industrial zone as detergent, foamer or emulsifier.
The sulfate salts are usually prepared by reaction of the hydroxyl group with a sulfating agent and neutralization of the sulfate product with base. For example, US4217296A discloses a process for preparing a mixture of sulfate salts of Cio-20 linear alkyl glyceryl ether alcohols by reacting a stoichiometric excess of &.20 linear alkyl alcohol with glycidol predissolved in hexyl acetate to selectively produce Cio-20 linear alkyl glyceryl ether alcohols containing 1-3 glyceryl units, sulfating said ether alcohols, and neutralizing the sulfates with base. Regarding the preparation of alkyl glyceryl ether alcohols, it is known that certain of such compounds may be prepared by reacting the corresponding aliphatic alcohol and glycidol. However, in this method, an alkali is used as catalyst which tends to have some problems such as low conversion of the alcohol and large impurity for removal of unreacted alcohol. On the other hand, working with glycidol has the drawback that the production of glycidol is difficult and
expensive and that it is difficult to prevent the glycidol from self-polymerizing.
WO 03104199A2 discloses a process for producing an organic catalyst comprising preparing a cyclic sulfate of monoalkyl glyceryl ether from alkyl glycidyl ether and SO3/D F as reactant in the presence of high toxic toluene as solvent and then reacting the cyclic sulfate with dihydroisoquinoline to form an organic catalyst comprising iminium or oxaziridinium moieties. This reference is silent to the production of the sulfate salt of monoalkyl glyceryl ether. There is still a need to provide a simple process for producing a non-cyclic sulfate of alkyl glyceryl ether with a high yield.
Summary of the Invention The objective of the present invention is to provide a process for preparing a sulfate salt of alkyl glyceryl ether, which is environmental friendly, simple and has a high yield.
Thereby, the present invention provides a process for preparing a sulfate salt of alkyl glyceryl ether, comprising:
a) reacting an alkyl glycidyl ether (AGE) with a gas containing S03, to produce an alkyl cyclic glycerol sulfate (CGS); and
b) hydrolyzing the alkyl cyclic glycerol sulfate with an alkaline solution to produce the sulfate salt of alkyl glyceryl ether (AGES). In the process according to the present invention, alkyl glycidyl ethers used as reactants are commercially available materials and it does not need to convert alkyl glycidyl ethers to alkyl glyceryl ethers. By this invention, alkyl glyceryl ether sulfates can be made directly from alkyl glycidyl ethers and S03 gas with a high selectivity and high yield. Specifically, the present process is a simple two steps process for producing alkyl glyceryl ether sulfate salt: the first step is
preparing a cyclic sulfate of alkyl glyceryl ether by reacting alkyl glycidyl ether and S03 gas; and the second step is directly neutralizing the cyclic sulfate of alkyl glyceryl ether in the reaction system to sulfate salts of alkyl glyceryl ether. In the process according to the present invention, the separation of the intermediate alkyl cyclic glycidyl ether is not needed. Moreover, in the present process, S03 is used in the form of gas and therefore no complex thereof, for example, S03/DMF or S03/pyridme will be involved in the reaction system. By the process according to the present invention, a highly pure alkyl glyceryl ether sulfate salt can be successfully obtained.
The present inventors have surprisingly found that a highly-selective reaction can be realized by reacting alkyl glycidyl ether and S03 gas and, after hydrolysis by alkaline solution, a high purity monoalkyl glyceryl ether sulfate salt can be successfully obtained.
The sulfate salt of alkyl glyceryl ether produced by the present invention has high water solubility and is excellent in foaming power, resistance to hard water, an ability to disperse scum. Moreover, it has low stimulation to the skin and excellent biodegradability and can be used as cleaning components excellent in cleaning and foaming abilities even at low temperatures.
When S03 gas is used as the gas containing SO3 and a NaOH solution is used for hydrolyzing, the reaction scheme may be as shown below:
The present invention provides a process for preparing a sulfate salt of alkyl glyceryl ether, comprising:
a) reacting an alkyl glycidyl ether with a gas containing S03 to produce an alkyl cyclic glycerol sulfate; and
b) hydrolyzing the alkyl cyclic glycerol sulfate with an alkaline solution to produce the sulfate salt of alkyl glyceryl ether.
Step fa)
The process according to the present invention is very simple and easy to be operated. Since the alkyl cyclic glycerol sulfate obtained in step a) can be directly reacted with an alkaline solution to produce the sulfate salt of alkyl glyceryl ether with a high purity, the separation of the intermediate alkyl cyclic glycerol sulfate from the reaction system in step a) can be omitted. Moreover, in the process according to the present invention, S03 gas is used in the form of pure gas or a gas mixture and therefore no impurity, for example, dimethyl formamide (DMF), pyridine or SO3/DMF complex or SO3 Pyridine complex, will be incorporated in the reaction medium.
According to some preferred embodiments, the above step a) is carried out under a temperature in a range of from about 10 to about 90°C.
Differents alkyl glycidyl ethers may be used as starting materials, as for example a mixture of at least two different glycidyl ethers. Preferably, the alkyl glyceryl ether is a compound of formula (I) or (II) :
R is an alkyl
n is comprised between 0 and 10
As used herein, unless stated otherwise, the term "alkyl" means a linear or branched alkyl group optionally substituted with one or more substituent selected from the group consisting of lower alkyl, lower alkoxy, lower alkylsulfanyl, lower alkylsulfenyl, lower alkylsulfonyl, oxo, hydroxy, mercapto, amino optionally substituted by alkyl, carboxy, carbamoyl optionally substituted by alkyl, aminosulfonyl optionally substituted by alkyl, nitro, cyano, halogen, or lower perfluoroalkyl, multiple degrees of substitution being allowed. Examples of "alkyl" as used herein include, but are not limited to, n-butyl, n-pentyl, isobutyl, isopropyl, and the like. Herein, the term "lower" means that the alkyl moiety of a group has 1 to 30, preferably 10 to 20, still more preferably 12 to 16 carbon atoms.
According to some preferred embodiments, the alkyl used in the present invention comprises 1-40, preferably 5-30, more preferably 10-16 carbon atoms. R is preferably an alkyl comprising from 1 to 40 carbon atoms.
R may be a linear or branched alkyl group optionally substituted with one or more substituent.
The sulfate salt of alkyl glyceryl ether is referably a compound of formula (ΠΙ) :
(III) wherein :
R is an alkyl
n is comprised between 0 and 10
X is H or S03M
Rl is OS03M, OH, or an alkoxy group
R2 is OSO3M, OH, or an alkoxy group
M is an alkaline earth metal
With the proviso that in one molecule at least one of Rl , R2 is OSO3M.
Rl and/or R2 are preferably an alkoxy group chosen from methoxyl, ethoxyl and propoxyl. According to some preferred embodiments, the gas containing S03 comprises at least 5% by volume of SO3 gas. The gas use din this step can notably be a S03 gas. The gas containing SO3 may also be a mixture of SO3 gas and an other gas, notably an inert gas. The inert gas is preferably selected from the group consisting of dry air, N2 or mixtures thereof.
The molar ratio of alkyl glycidyl ether / SO3 may be comprised between 1.0:0.2 to 1.0:2.0.
Step (b
According to some preferred embodiments, said alkaline solution is a solution of at least one selected from the group consisting of sodium hydroxide (NaOH), potassium hydroxide (KOH), sodium carbonate (Na2CO3), sodium bicarbonate (NaHCO3), sodium sulfite ( a2SO), sodium bisulfite (NaHS03), potassium carbonate (K2C03), potassium bicarbonate (KHCO3), potassium sulfite (K2SO3), potassium bisulfite (KHS03), ammonia, ammonium hydroxide, MeONa, EtONa or mixtures thereof. More preferably, said alkaline solution is an aqueous solution of NaOH.
This reaction is preferably run at a temperature comprised between 30-150 °C with an alkaline solution in solvent; such as water, methanol, ethanol, propanol, butanol, acetonitrile, actone, dimethyl sulfoxide, dimethylformamide, tetrahydrofuran,
diethylether, chloroform, glycol, ethylene glycol dimethyl ether, dioxane or mixture of them.
The invention will be illustrated below with the aid of examples. Embodiment of the Present Invention
The materials used in the following examples were summarized in the following table:
The characterization of products:
Ή-NMR analysis conditions:
Solvent: MeOD (deuteriated methanol)
The chemical shifts for monoalkyi glycerol ether sulfates are: 0.8-4.5ppm.
HPLC-MS analysis conditions:
Column: Merck RP-18e, 2mm*50mm
Flow: 1.8ml/min
Column temperature: 40 "C
Retention time for MAGES is: 1.3-2.3min
Example 1 :
A 100ml three necked round-bottom flask was equipped with a cooling system and a gas inlet. 0.1 mol alkyl (Ci2) glycidyl ether was added to the flask, and reacted with 0.103mol of sulfur trioxide at a temperature of 80°C. The sulfur trioxide was driven off by heating from a corresponding quantity of 65% by weight oleum, diluted with nitrogen to a concentration of 5% by volume. The sulfur trioxide was introduced to the mixture of alkyl glycidyl ether over 30mins. When the reaction was finished, the crude sulfatization product alkyl cyclic glycerol sulfate (ACGS) was obtained. Then the crude ACGS was neutralized with aqueous NaOH at 80 °C for 24hrs. The water was removed, anionic surfactant-alkyl glyceryl ether sulfate, sodium salt was obtained. The product was determined by HPLC/MS and 1H-NMR analysis. The yield of reaction is 90% based on starting alkyl glycidyl ether.
¾ NMR (MeOD, 500 MHz), δ: 3.98-4.05 (m, 3H), 3.47-3.53 (m, 4H), 1.56-1.59 (q, 2H), 1.30-1.35 (m, 18H), 0.9 l (t, 3H).
Example 2
A 100ml three necked round-bottom flask was equipped with a cooling system and a gas inlet. 0.1 mol alkyl (C12.i4) glycidyl ether was added to the flask, and reacted with 0.103mol of sulfur trioxide at a temperature of 80 °C . The sulfur trioxide was driven off by heating from a corresponding quantity of 65% by weight oleum, diluted with nitrogen to a concentration of 5% by volume. The sulfur trioxide was introduced to the mixture of alkyl glycidyl ether over 30mins. When the reaction was finished, the crude sulfatization product alkyl cyclic glycerol sulfate (ACGS) was obtained. Then the crude ACGS was neutralized with aqueous NaOH at 80 °C for 24hrs. The water was removed, anionic surfactant-alkyl glyceryl ether sulfate, sodium salt was obtained. The product was determined by HPLC/MS and Ή-NMR analysis. The yield of reaction is 85% based on starting alkyl glycidyl ether.
Example 3
A 100ml three necked round-bottom flask was equipped with a cooling system and a gas inlet. 0.1 mol alkyl (Cg) glycidyl ether was added to the flask, and reacted with 0.103mol of sulfur trioxide at a temperature of 80C . The sulfur trioxide was driven off by heating from a corresponding quantity of 65% by weight oleum, diluted with nitrogen to a concentration of 5% by volume. The sulfur trioxide was introduced to the mixture of alkyl glycidyl ether over 30mins. When the reaction was finished, the crude sulfatization product alkyl cyclic glycerol sulfate (ACGS) was obtained. Then the crude ACGS was neutralized with aqueous NaOH at 80 °C for 24hrs. The water was removed, anionic surfactant-alkyl glyceryl ether sulfate, sodium salt was obtained. The product was determined by HPLC/MS and Ή-NMR analysis.
Example 4: neutralized by MeONa in THF
A 100ml three necked round-bottom flask was equipped with a cooling system and a gas inlet. 0.1 mol alkyl (C]2) glycidyl ether was added to the flask, and reacted
with 0.103mol of sulfur trioxide at a temperature of 80 °C . The sulfur trioxide was driven off by heating from a corresponding quantity of 65% by weight oleum, diluted with nitrogen to a concentration of 5% by volume. The sulfur trioxide was introduced to the mixture of alkyl glycidyl ether over 30mins. When the reaction was finished, the crude sulfatization product alkyl cyclic glycerol sulfate (ACGS) was obtained. Then the crude ACGS was neutralized with MeONa in THF at 55 degree for 24hrs. THF was removed, anionic surfactant- alkyl glyceryl ether sulfate, sodium salt was obtained. The product was determined by HPLC/MS and 1H-NMR analysis. The total yield of two step reactions is 70% based on starting alkyl glycidyl ether.
Example 5: The sulfation of AGE derivatives
A 100ml three necked round-bottom flask was equipped with a cooling system and a gas inlet. 0.1 mol 2-((2-(dodecyloxy)ethoxy)methyl)oxirane was added to the flask, and reacted with 0.103mol of sulfur trioxide at a temperature of 80°C . The sulfur trioxide was driven off by heating from a corresponding quantity of 65% by weight oleum, diluted with nitrogen to a concentration of 5% by volume. The sulfur trioxide was introduced to the mixture of 2-((2-(dodecyloxy)ethoxy)methyl)oxirane over 30mins. When the reaction was finished, the crude sulfatization product alkyl cyclic glycerol sulfate (ACGS) was obtained. Then the crude ACGS was neutralized with aqueous NaOH at 80 °C for 24hrs. The water was removed, anionic surfactant-alkyl glyceryl ether sulfate, sodium salt was obtained. The product was determined by HPLC/MS and Ή-NMR analysis.
Claims
1. A process for producing a sulfate salt of alkyl glyceryl ether, comprising:
a) reacting an alkyl glycidyl ether with a gas containing S03 to produce an alkyl cyclic glycerol sulfate; and
b) hydrolyzing the alkyl cyclic glycerol sulfate with an alkaline solution to produce the sulfate salt of alkyl glyceryl ether.
2. The process according to claim 1, wherein the step a) is carried out under a temperature of about 10 to 90°C.
3. The process according to claim 1, wherein the alkyl glyceryl ether is a compound of formula (I) or (II) :
wherein :
R is an alkyl
n is comprised between 0 and 10.
4. The process according to claim 3, wherein R is an alkyl comprising from 1 to 40 carbon atoms.
5. The process according to claim 3 or 4, wherein R is a linear or branched alkyl group optionally substituted with one or more substituent.
6. The process according to claim 1, wherein the sulfate salt of alkyl glyceryl ether is a compound of formula (ΓΠ) : 
(Hi) wherein :
is an alkyl
n is comprised between 0 and 10
X is H or S03M
Rl is OSO3M, OH, or an alkoxy group
R2 is OSO3M, OH, or an alkoxy group
M is an alkaline earth metal
With the proviso that in one molecule at least one of Rl, R2 is OS03M.
7. The process according to claim 1, wherein the molar ratio of alkyl glycidyl ether / S03 is comprised between 1 ,0:0.2 to 1.0:2.0.
8. The process according to claim 1, wherein the gas containing SO3 comprising at least 5% by volume of S03 gas.
9. The process according to claim 4, wherein the gas containing S03 being a mixture of SO3 gas and an inert gas.
10. The process according to claim 5, wherein said inert gas is selected from the group consisting of dry air, N2 or mixtures thereof.
11. The process according to any one of claims 1 to 6, wherein said alkaline solution is a solution of at least one selected from the group consisting of sodium hydroxide, potassium hydroxide, ammonia, ammonium hydroxide, MeONa, EtONa or mixtures thereof.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/CN2012/071335 WO2013123633A1 (en) | 2012-02-20 | 2012-02-20 | Process for producing a sulfate salt of alkyl glyceryl ether |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/CN2012/071335 WO2013123633A1 (en) | 2012-02-20 | 2012-02-20 | Process for producing a sulfate salt of alkyl glyceryl ether |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2013123633A1 true WO2013123633A1 (en) | 2013-08-29 |
Family
ID=49004910
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/CN2012/071335 WO2013123633A1 (en) | 2012-02-20 | 2012-02-20 | Process for producing a sulfate salt of alkyl glyceryl ether |
Country Status (1)
| Country | Link |
|---|---|
| WO (1) | WO2013123633A1 (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003104199A2 (en) * | 2002-06-06 | 2003-12-18 | The Procter & Gamble Company | Organic catayst with enhanced solubility |
-
2012
- 2012-02-20 WO PCT/CN2012/071335 patent/WO2013123633A1/en active Application Filing
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003104199A2 (en) * | 2002-06-06 | 2003-12-18 | The Procter & Gamble Company | Organic catayst with enhanced solubility |
Non-Patent Citations (1)
| Title |
|---|
| POORKER, CAROL S. ET AL.: "The facile addition offluorosulfuric acid to an epoxide", TETRAHEDRON LETTERS, vol. 26, no. 52, 1985, pages 6405 - 8, XP055081780 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101688153B (en) | Surfactant composition | |
| CN101108327A (en) | Alkyl- fragrant benzyl- polyethenoxy ether anionic surfactant and method of preparing the same and use thereof | |
| CN104053644A (en) | Process For Preparing An Internal Olefin Sulfonate | |
| CN108026489B (en) | Anionic surfactants | |
| JPS6072852A (en) | Ether sulfonate | |
| EP0011311B1 (en) | Alkyl glyceryl ether sulfate salts, process for their preparation and composition of matter containing them | |
| US3376333A (en) | Sulfuric acid esters of linear secondary alcohol ethoxylates and salts thereof and method of producing same | |
| CN107955045B (en) | Alkyl glycoside alkyl succinic acid monoester sulfonate surfactant and preparation method thereof | |
| TWI383987B (en) | Novel process for the preparation of 5-amino-3h-thiazolo[4,5-d]pyrimidin-2-one | |
| AU642949B2 (en) | Process for the preparation of beta-substituted sulphonic acids and/or sulphonates | |
| CN102712593A (en) | Method for producing 2-amino-4-(trifluoromethyl)pyridine | |
| WO2013123633A1 (en) | Process for producing a sulfate salt of alkyl glyceryl ether | |
| CN104628653B (en) | The method of synthesizing rosuvastatin spit of fland calcium key intermediate | |
| US3607778A (en) | Anionic surface-active agents from epoxyalkanes and method for their production | |
| JP2907517B2 (en) | 2- or 3-chain bihydrophilic compound | |
| JPWO2014034681A1 (en) | Process for producing polyoxyethylene alkyl ether sulfate | |
| US20120004431A1 (en) | 2-Alkyl alkoxylated alcohol sulfonate | |
| KR890001967A (en) | Sulfated hydroxy mixed ethers, preparation methods thereof and uses thereof | |
| TWI483934B (en) | 4,6-dialkoxy-2-cyanomethylpyrimidine and a synthetic intermediate | |
| KR100695577B1 (en) | Anionic surfactants containing sulfonyl-imide group | |
| CN105693581A (en) | Method for preparing methylmercaptodiafenthiuron | |
| CN103301781A (en) | Two-step preparation method of alkyl alcohol/alkenyloxylated alkylalcohol/alkylphenol sulfonate | |
| CN104744273A (en) | Preparation method for N-[2-(2-hydroxyethoxy)-4-nitrophenyl] ethanol amine | |
| CN112759535B (en) | Preparation method of PF-06651600 intermediate | |
| US3230250A (en) | Preparation of 1-hydroxy-2-alkane-sulfonates |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 12869358 Country of ref document: EP Kind code of ref document: A1 |
|
| NENP | Non-entry into the national phase |
Ref country code: DE |
|
| 122 | Ep: pct application non-entry in european phase |
Ref document number: 12869358 Country of ref document: EP Kind code of ref document: A1 |