CA2060049A1 - Process for the preparation of dialkylaminopropanediol - Google Patents
Process for the preparation of dialkylaminopropanediolInfo
- Publication number
- CA2060049A1 CA2060049A1 CA002060049A CA2060049A CA2060049A1 CA 2060049 A1 CA2060049 A1 CA 2060049A1 CA 002060049 A CA002060049 A CA 002060049A CA 2060049 A CA2060049 A CA 2060049A CA 2060049 A1 CA2060049 A1 CA 2060049A1
- Authority
- CA
- Canada
- Prior art keywords
- water
- reaction
- dialkylamine
- temperature
- dimethylamine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 238000000034 method Methods 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 56
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims abstract description 53
- 238000006243 chemical reaction Methods 0.000 claims abstract description 49
- 125000005265 dialkylamine group Chemical group 0.000 claims abstract description 35
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims abstract description 4
- HUXDTFZDCPYTCF-UHFFFAOYSA-N 1-chloropropane-1,1-diol Chemical compound CCC(O)(O)Cl HUXDTFZDCPYTCF-UHFFFAOYSA-N 0.000 claims abstract 2
- 239000000203 mixture Substances 0.000 claims description 26
- 239000007795 chemical reaction product Substances 0.000 claims description 10
- 239000000126 substance Substances 0.000 abstract description 2
- SSZWWUDQMAHNAQ-UHFFFAOYSA-N 3-chloropropane-1,2-diol Chemical compound OCC(O)CCl SSZWWUDQMAHNAQ-UHFFFAOYSA-N 0.000 description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 18
- 238000009835 boiling Methods 0.000 description 10
- ZVXMMOSAYTZLSG-UHFFFAOYSA-N 1-(dimethylamino)propane-1,1-diol Chemical compound CCC(O)(O)N(C)C ZVXMMOSAYTZLSG-UHFFFAOYSA-N 0.000 description 9
- 238000004821 distillation Methods 0.000 description 8
- 230000035484 reaction time Effects 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- QCMHUGYTOGXZIW-UHFFFAOYSA-N 3-(dimethylamino)propane-1,2-diol Chemical compound CN(C)CC(O)CO QCMHUGYTOGXZIW-UHFFFAOYSA-N 0.000 description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000007858 starting material Substances 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 3
- -1 amine compounds Chemical class 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical group 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 150000000185 1,3-diols Chemical class 0.000 description 1
- RJUGWLIJYSWLRS-UHFFFAOYSA-N 1-amino-2,2-dimethylpropane-1,1-diol Chemical compound CC(C(O)(O)N)(C)C RJUGWLIJYSWLRS-UHFFFAOYSA-N 0.000 description 1
- UXDCXJABIPXRIV-UHFFFAOYSA-N 1-amino-2-ethyl-2-methylbutane-1,1-diol Chemical compound C(C)C(C(O)(O)N)(C)CC UXDCXJABIPXRIV-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 150000007514 bases Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- PRAHCKGOTFKWKD-UHFFFAOYSA-N dimethyl(propyl)azanium;chloride Chemical compound Cl.CCCN(C)C PRAHCKGOTFKWKD-UHFFFAOYSA-N 0.000 description 1
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229960000443 hydrochloric acid Drugs 0.000 description 1
- 235000011167 hydrochloric acid Nutrition 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000036647 reaction Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/04—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reaction of ammonia or amines with olefin oxides or halohydrins
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C215/00—Compounds containing amino and hydroxy groups bound to the same carbon skeleton
- C07C215/02—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
- C07C215/04—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being saturated
- C07C215/06—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being saturated and acyclic
- C07C215/10—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being saturated and acyclic with one amino group and at least two hydroxy groups bound to the carbon skeleton
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Abstract of the disclosure Process for the preparation of dialkylaminopropanediol The novel process is based on the reaction of a dialkyl-amine, preferably dimethylamine or diethylamine, with a monohalopropanediol, preferably monochloropropanediol, in the presence of water. The reaction is carried out in the presence of 25 to 70% by weight of water and at a tem-perature of 20 to 80°C, the dialkylamine being employed in an amount of at least 2.5 mol per mole of monohalopro-panediol. Using the novel process, a high space-time yield and also a high chemical yield of virtually pure dialkylaminopropanediol are obtained.
Description
HOECHST AgTIENGESELLSCHAFT HOE 91/F 901 Dr.GL-nu Werk Gendorf Process for the preparation of dialkylaminopropanediol Description The invention relates to a process for the preparation of dialkylaminopropanediol by reaction of monohalopropane-diol with excess dialkylamine in the presence of water.
Such a process is described in US Patent 2,147,226,monochloropropanediol (glycerol monochlorohydrin) and dimethylamine being employed as starting compounds. The equation below using said starting compounds is intended to illustrate the reactions CH2-Cl CH2-NtCH3)2 CX-O~ + ICH~)2NH C~-OH ~ XCl According to ~S Patent 2,147,226, the dimethylamine is employed in an amount of up to 1.5 mol per mole of glycerol monochlorohydrin. The reaction, which occur~ in an exothermic manner, is carried out at a temperature of 20 to 50C and in the presence of a relatively large amount of water (in the exemplary embodiments, the dimethylamine is employed in the form of a 24.5% strength aqueous solution, i.e. 75.5% by weight of water, relative to the mixture of dimethylamine and water). The hydro-chloric acid liberated during the reaction is bound by an alkali metal hydroxide which is likewise employed in the form of an aqueous solution. This process is thus carried out using a low concentration of dimethylamine and consequently using a large amount of water. This repre-sents a substantial deficiency of this process. A further disadvantage is that the reaction time is relatively long and the yield of dimethylaminopropanediol, relative to glycerol monochlorohydrin, is low in spite of this. A
yield of 98% of theory admittedly results from the single example. However, it was not possible to confirm this high value by reworking the example.
In said US Patent 2,147,226, prior art is mentioned at the start according to which dimethylaminopropanediol has been prepared in the laboratory by heating glycerol monochlorohydrin and dimethylamine to 100C in a closed tube. Undesired by-products are formed at this relatively high temperature. Compared with this anhydrous manner of preparation, that of said US patent i6 thus more advantageous.
The invention is accordingly based on the object of improving the process known from US Patent 2,147,226 and based on a low reaction temperature, in particular with respect to amount of water, reaction time and yield.
The process according to the invention comprises employ-ing the dialkylamine in an amount of at least 2.5 mol per mole of monohalopropanediol, preferably in an amount of 3 to 6 mol per mole of monohalopropanediol, and carrying out the reaction in the presence of 25 to 70% by weight of water, preferably 30 to 60% by weight of water, relative to the mixture of dialkylamine and water, and at a temperature of 20 to 80C, preferably 30 to 60C, and recovering the desired dialkylaminopropanediol from the reaction product.
In the process according to the invention, the reaction of the dialkylamine and the halopropanediol is thus carried out in the presence of a very specific amount of water. Thus, reaction at the given temperature in the case of less than 25% of water, relative to the mixture of dialkylamine and water, simply comes to a stop after a reaction time of greater or lesser length. Using more than 70~ by weight of water, a relatively short reaction time is in fact achieved, but the space-time yield is impaired. The amount of water (the aqueous medium) thus represents a critical quantity of the process according 20~0049 to the invention and i8, as stated above, 25 to 70% by weight, preferably 30 to 60~ by weight, percentages by weight relative to the sum of dialkylamine and water employed.
Additionally, in the proces6 according to the invention the dialkylamine is employed in an amount of at least 2.5 mol per mole of halopropanediol. Undesired by-pro-ducts are formed even at a relatively low molar ratio.
The upper amount of dialkylamine can vary within a wide range. As a rule, not more than 6 mol of dialkylamine will be employed per mole of halopropanediol. The amount of dialkylamine is therefore preferably 3 to 6 mol of dialkylamine per mole of monohalopropanediol.
The reaction temperature suited to the stated amount of water and amount of dialkylamine to achieve the desired effect is 20 to 80C. Below 20C, the reaction time is already relatively long and above 80C the formation of by-products can occur. The preferred reaction temperature is therefore 30 to 60C.
As far as the binding of the hydrohalic acid formed in the reaction is concerned, the amine compounds present are used for this. The hydrohalic acid is thus bound in the process according to the invention by the amine present in the system itself and not by alkali metal hydroxides (i.e. extraneous basic compounds), as in the prior art.
To carry out the process according to the invention, the dialkylamine and the halopropanediol are brought into contact in the stated molar ratio and in the stated amount of water and at the stated reaction temperature.
The manner of bringing into contact is not critical per se. The following forms of implementation (1 to 4) are preferred: (1) all of the dialkylamine, halopropandediol and water are added to a reaction vessel and kept at the temperature stated until all the halopropanediol has been reacted; (2) all of the dialkylamine and the water are initially introduced. The mixture i8 brought to reaction temperature, after which the halopropanediol is added thereto as ~uch (in portions or continuously) at this S temperature. After addition, the mixture i9 additionally kept at reaction temperature for the subsequent reaction;
Such a process is described in US Patent 2,147,226,monochloropropanediol (glycerol monochlorohydrin) and dimethylamine being employed as starting compounds. The equation below using said starting compounds is intended to illustrate the reactions CH2-Cl CH2-NtCH3)2 CX-O~ + ICH~)2NH C~-OH ~ XCl According to ~S Patent 2,147,226, the dimethylamine is employed in an amount of up to 1.5 mol per mole of glycerol monochlorohydrin. The reaction, which occur~ in an exothermic manner, is carried out at a temperature of 20 to 50C and in the presence of a relatively large amount of water (in the exemplary embodiments, the dimethylamine is employed in the form of a 24.5% strength aqueous solution, i.e. 75.5% by weight of water, relative to the mixture of dimethylamine and water). The hydro-chloric acid liberated during the reaction is bound by an alkali metal hydroxide which is likewise employed in the form of an aqueous solution. This process is thus carried out using a low concentration of dimethylamine and consequently using a large amount of water. This repre-sents a substantial deficiency of this process. A further disadvantage is that the reaction time is relatively long and the yield of dimethylaminopropanediol, relative to glycerol monochlorohydrin, is low in spite of this. A
yield of 98% of theory admittedly results from the single example. However, it was not possible to confirm this high value by reworking the example.
In said US Patent 2,147,226, prior art is mentioned at the start according to which dimethylaminopropanediol has been prepared in the laboratory by heating glycerol monochlorohydrin and dimethylamine to 100C in a closed tube. Undesired by-products are formed at this relatively high temperature. Compared with this anhydrous manner of preparation, that of said US patent i6 thus more advantageous.
The invention is accordingly based on the object of improving the process known from US Patent 2,147,226 and based on a low reaction temperature, in particular with respect to amount of water, reaction time and yield.
The process according to the invention comprises employ-ing the dialkylamine in an amount of at least 2.5 mol per mole of monohalopropanediol, preferably in an amount of 3 to 6 mol per mole of monohalopropanediol, and carrying out the reaction in the presence of 25 to 70% by weight of water, preferably 30 to 60% by weight of water, relative to the mixture of dialkylamine and water, and at a temperature of 20 to 80C, preferably 30 to 60C, and recovering the desired dialkylaminopropanediol from the reaction product.
In the process according to the invention, the reaction of the dialkylamine and the halopropanediol is thus carried out in the presence of a very specific amount of water. Thus, reaction at the given temperature in the case of less than 25% of water, relative to the mixture of dialkylamine and water, simply comes to a stop after a reaction time of greater or lesser length. Using more than 70~ by weight of water, a relatively short reaction time is in fact achieved, but the space-time yield is impaired. The amount of water (the aqueous medium) thus represents a critical quantity of the process according 20~0049 to the invention and i8, as stated above, 25 to 70% by weight, preferably 30 to 60~ by weight, percentages by weight relative to the sum of dialkylamine and water employed.
Additionally, in the proces6 according to the invention the dialkylamine is employed in an amount of at least 2.5 mol per mole of halopropanediol. Undesired by-pro-ducts are formed even at a relatively low molar ratio.
The upper amount of dialkylamine can vary within a wide range. As a rule, not more than 6 mol of dialkylamine will be employed per mole of halopropanediol. The amount of dialkylamine is therefore preferably 3 to 6 mol of dialkylamine per mole of monohalopropanediol.
The reaction temperature suited to the stated amount of water and amount of dialkylamine to achieve the desired effect is 20 to 80C. Below 20C, the reaction time is already relatively long and above 80C the formation of by-products can occur. The preferred reaction temperature is therefore 30 to 60C.
As far as the binding of the hydrohalic acid formed in the reaction is concerned, the amine compounds present are used for this. The hydrohalic acid is thus bound in the process according to the invention by the amine present in the system itself and not by alkali metal hydroxides (i.e. extraneous basic compounds), as in the prior art.
To carry out the process according to the invention, the dialkylamine and the halopropanediol are brought into contact in the stated molar ratio and in the stated amount of water and at the stated reaction temperature.
The manner of bringing into contact is not critical per se. The following forms of implementation (1 to 4) are preferred: (1) all of the dialkylamine, halopropandediol and water are added to a reaction vessel and kept at the temperature stated until all the halopropanediol has been reacted; (2) all of the dialkylamine and the water are initially introduced. The mixture i8 brought to reaction temperature, after which the halopropanediol is added thereto as ~uch (in portions or continuously) at this S temperature. After addition, the mixture i9 additionally kept at reaction temperature for the subsequent reaction;
(3) all of the halopropanediol and the water are initially introduced. The mixture i6 brought to reaction temperature, after which the dialkylamine is added thereto as such at this temperature. After the addition, the mixture is additionally kept at reaction temperature for the subsequent reaction (4) all of the halopropanediol is initially introduced and brought to reaction temperature, after which the dialkylamine and the water are added thereto at this temperature, separately from one another or together in the form of an aqueous dialkylamine solution. After the addition, the mixture is additionally kept at reaction temperature for the subsequent reaction. The reaction between the dialkylamine and halopropanediol is exothermic. In the case of a low-boiling dialkylamine compound, such as dimethylamine, which has a boiling point of 7C at normal pressure, the reaction is carried out in a pressure vessel, as more or less high vapor pressures have to be taken into account at said reaction temperatures. The reaction time is 2 to 10 hours and in particular depends on the amount of water and reaction temperature chosen.
If it is desired to work up the reaction product obtained by the process according to the invention and to recover the dialkylaminopropanediol compound, this is preferably carried out by the following method: the dialkylamine and the water are first removed by distillation from the reaction product, which is essentially composed of dialkylaminopropanediol . HX (X = halogen), the dialkyl-amine employed in excess and water, after which thedialkylaminopropanediol hydrohalide product is present in high purity. To liberate the dialkylaminopropanediol, the hydrohalide compound is treated for neutralization 206~049 purposes with about 1 molar equivalent of alkali metal hydroxide, preferably potassium hydroxide or sodium hydroxide, expediently in the form of a 30 to 60% by weight aqueous solution, the temperature of the mixture being kept at preferably 20 to 60C by cooling. The dialkylaminopropanediol (expediently after filtering off or centrifuging off the main paxt of the salt) can be recovered simply by distillative working up of the mixture of dialkylaminopropanediol, water and salt then present. As the dialkylaminopropanediol is present in high purity in said mixture, the distillative isolation of the dialkylaminopropanediol iB often not necessary at all. In this case, the relatively complicated steps, filtration or centrifugation, if necessary washing, and finally distillation, can be dispensed with. The above-mentioned dialkylaminopropanediol hydrohalide which is obtained in high purity is also already an advantageous starting material for subsequent reactions.
The starting compounds of the reaction according to the invention are monohalopropanediol and dialkylamine.
Dialkylamine in the context of the present invention is understood as meaning the lower dialkylamines, preferably dimethylamine and diethylamine. All these compounds are known and commercially available. Said dialkylamines are liquids having a boiling point of 7C (dimethylamine) and 50C (diethylamine) at normal pressure. The particularly preferred dialkylamine is dimethylamine. As is known, halopropanediol exists in two structural forms, in particular as 3-halopropane-1,2-diol or as 2-halopropane-1,3-diol, the first mentioned compound being much the more frequent. The formulae below are intended to illu-strate the two structures, where X i8 a halogen:
f~2-X ~a-~
CH-OH CH-X
l~2 ~ CHa-~
3-halopropane- 2-halopropane-1,2-diol 1,3-diol.
The halopropanediols are also liquids. As chlorine is the usual halogen, 3-chloropropane-1,2-diol, whose boiling under normal pressure is 213C, i8 the preferred com-pound. The dialkylaminopropanediol prepared by the process according to the invention is therefore prefer-ably a dimethylaminopropanediol, in particular 3-dimethylaminopropane-1,2-diol.
The process according to the invention has a number of advantages compared with the prior art. The reaction can be carried out with a substantially higher concentration of dialkylamine or, expressed in another way, with a substantially lower water content. The reaction time is additionally much shorter. A high space-time yield is obtained because of the higher dialkylamine concentration and the shorter reaction time. The chemical yield of dialkylaminopropanediol, relative to glycerol monohalo-hydrin employed, is also very high. As a rule, it is 91to 97%. A further advantage of the process according to the invention is the high purity of the dialkylaminopro-panediol obtained. It can frequently be reused without distillative working up. In a distillative fine purifica-tion, only very little residue is produced. Said advan-tages also result when a crude halopropanediol is used as starting material, i.e. for example a chloropropanediol as is obtained by hydrolysis of epichlorohydrin, in particular without further purification of the hydrolysis product, can rather be employed as such. All these surprising effects of the process according to the invention obviously result from the combination of the 20600~g measures described. The process according to the invention can additionally be carried out batchwise or continuously.
Dialkylaminopropanediol6, such a6 dimethyl- and diethyl-aminopropanediol, are useful intermediates because of their trifunctionality.
The invention will now be illustrated in greater detail by examples.
Example 1 900.0 g (20.0 mol) of dimethylamine and 385.7 g of water (i.e. 30.0% by weight of water, relative to dimethylamine plus water) were initially introduced into a reaction vessel and warmed to 30C with stirring (the following operations were also carried out with stirring; this also applies to all other examples). 734.8 g (6.65 mol) of 3-chloropropane-1,2-diol were continuously added to this mixture in the course of about 2 hours while maintaining a temperature of 30 to 35C. After the addition of chloropropanediol, the mixture was kept at said tempera-ture for a further 7 hours for subsequent reaction, after which all of the chloropropanediol had reacted (the pressure in the reaction vessel, which essentially results from the vapor pressure of the dimethylamine, was 0.15 to 0.20 MPa).
The working up of the reaction product was carried out as follows: the excess dimethylamine and a large part of the water were first removed from the reaction product (contents of the reaction vessel) by distillation at normal pressure and a temperature of at most 115C. The water was further removed by distillation in a water pump vacuum at 0.005 MPa. The mixture of dimethylaminopropane hydrochloride and water then present (about 2% by weight) was treated in the course of one hour with a stoichiomet-ric amount of sodium hydroxide, relative to chloropropanediol employed (i.e. 6.65 mol of NaOH), in the form of an approximately 50% strength by weight solution whilst stirring and maintaining a temperature of at most 50C to release the dimethylaminopropanediol from the hydrochloride. The precipitated salt was removed from the mixture composed of dimethylaminopropanediol, water and precipitated sodium chloride by filtration at room temperature. The filter cake was washed three times with isopropanol (250 ml, 200 ml and 150 ml), after which the individual filtrates were combined. The water and the isopropanol were removed from the mixture of dimethyl-aminopropanediol, water and isopropanol by distillation in a water pump vacuum at a temperature of up to 100C.
The 3-dimethylaminopropane-1,2-diol of boiling point 74 to 75C at 122 Pa was then distilled over. 734.3 g (6.16 mol) of pure product were obtained, i.e. 92.6% of the theoretical yield. The product had a purity of 99.8%.
Example 2 900.0 g (20.0 mol) of dimethylamine and 385.7 g of water (i.e. 30.0% by weight of water, relative to dimethylamine plus water) were initially introduced into a reaction vessel and heated to 40C with stirring. 553.0 g (5.0 mol) of 3-chloropropane-1,2-diol were continuously added to this mixture in the course of approximately 1.5 hours while maintaining a temperature of 40 to 50C.
After the addition of the chloropropanediol, the mixture was kept at said temperature for a further 5 hours for subsequent reaction, after which all of the chloro-propanediol had reacted (the pressure in the reaction vessel was approximately 0.2 NPa). The reaction product was worked up analogously to Example 1. 559.0 g (4.69 mol) of 3-dimethylaminopropane-1,2-diol of boiling point 93C at 0.7 to 0.9 kPa were obtained, i.e. 93.8% of theory. The dimethylaminopropanediol had a purity of 99.5%.
g Example 3 900.0 g (20.0 mol) of dimethylamine, 900.0 g of water (i.e. 50.0% by weight of water, relative to dimethylamine plus water) and 443.0 g (4.0 mol) of 3-chloropropane-1,2-diol were initially introduced into a reaction vesselwith ~tirring and cooling and ad~usted to a temperature of 50 to 55C. The mixture was kept at said temperature for 6 hours with stirring. After this time, all of the chloropropanediol had reacted.
The reaction product was worked up analogously to Example 1. 464.8 g (3.90 mol) of 3-dimethylaminopropane-1,2-diol of boiling point 89C at 0.6 to 0.8 kPa were obtained, i.e. 97.5% of theory. The dimethylaminopropanediol had a purity of 99.5%.
Example 4 443.0 g (4.0 mol) of 3-chloropropane-1,2-diol were initially introduced into a reaction vessel and heated to 40C with stirring. 900.0 g (20.0 mol) of dimethylamine and 1,350.0 g of water (i.e. 60% by weight of water, relative to dimethylamine plus water) were continuously added simultaneously and separately from one another to the heated chloropropanediol in the course of 1 hour while maintaining a temperature of 40 to 45C. After this addition, the mixture was kept at said temperature for a further 4 hours for subsequent reaction, after which all of the chloropropanediol had reacted.
The reaction product was worked up analogously to Example 1. 463.6 g (3.89 mol) of 3-dimethylaminopropane-1,2-diol of boiling point 93C at 0.7 to 0.9 kPa were obtained, i.e. 97.3% of theory. The dimethylaminopropanediol had a purity of 99.5%.
Example 5 443.0 g (4.0 mol) of 3-chloropropane-1,2-diol were initially introduced into a reaction vessel and heated to 35C with stirring. 450.0 g (10.0 mol) of dimethylamine and 675.0 g of water (i.e. 60% by weight of water, relative to dimethylamine plus water) were continuously added simultaneously and separately from one another to the heated chloropropanediol in the course of 1.5 hours while maintaining a temperature of 35 to 40C. After this addition, the mixture was kept at said temperature for a further 5 hours for subsequent reaction, after which all of the chloropropanediol had reacted.
The reaction product was worked up analogously to Example 1. 435.1 g (3.65 mol) of 3-dimethylaminopropane-1,2-diol of boiling point 89C at 0.6 to 0.8 kPa were obtained, i.e. 91.3% of theory. The dimethylaminopropanediol had a purity of 99.5~.
Comparison example (reworking of the example of US Patent 2,147,226) 3.986 kg of a 24.5% strength aqueous dimethylamine solution (i.e. 0.977 kg or 21.71 mol of dimethylamine) and 0.679 kg of a 40% strength aqueous sodium hydroxide solution (i.e. 0.272 kg or 6.80 mol of NaOH) were mixed together in a reaction vessel with stirring and cooling.
Altogether 1.812 kg of glycerol l-monochlorohydrin (i.e.
16.40 mol) were added in 0.091 kg portions in the course of 15 minutes in each case. The reaction mixture was kept at 20 to 40C the whole time. The pressure in the reac-tion vessel rose to 0.1 MPa. The mixture was allowed to stand for 24 hours, after which 0.679 kg of a 40%
strength aqueous sodium hydroxide solution (i.e. 0.272 kg or 6.80 mol of NaOH) were added thereto. The reaction vessel was then opened and the mixture was heated in stages to 105C, the unreacted dimethylamine being removed by distillation. The water was removed from the residual mixture by distillation at a pressure of 6.7 kPa. The distillation residue was cooled to 40C and mixed with 1.520 kg of methanol, whereupon sodium chloride precipitated from the mixture. The salt was removed in a centrifuge, after which the methanol was recovered from the liquid by di~tillation at a pres~ure of 6.7 kPa. 1.295 kg (10.86 mol) of 3-dimethylamino-propane-1,2-diol of boiling point 74 to 75C at 122 Pa were obtained, i.e. 66.3~ of theory.
If it is desired to work up the reaction product obtained by the process according to the invention and to recover the dialkylaminopropanediol compound, this is preferably carried out by the following method: the dialkylamine and the water are first removed by distillation from the reaction product, which is essentially composed of dialkylaminopropanediol . HX (X = halogen), the dialkyl-amine employed in excess and water, after which thedialkylaminopropanediol hydrohalide product is present in high purity. To liberate the dialkylaminopropanediol, the hydrohalide compound is treated for neutralization 206~049 purposes with about 1 molar equivalent of alkali metal hydroxide, preferably potassium hydroxide or sodium hydroxide, expediently in the form of a 30 to 60% by weight aqueous solution, the temperature of the mixture being kept at preferably 20 to 60C by cooling. The dialkylaminopropanediol (expediently after filtering off or centrifuging off the main paxt of the salt) can be recovered simply by distillative working up of the mixture of dialkylaminopropanediol, water and salt then present. As the dialkylaminopropanediol is present in high purity in said mixture, the distillative isolation of the dialkylaminopropanediol iB often not necessary at all. In this case, the relatively complicated steps, filtration or centrifugation, if necessary washing, and finally distillation, can be dispensed with. The above-mentioned dialkylaminopropanediol hydrohalide which is obtained in high purity is also already an advantageous starting material for subsequent reactions.
The starting compounds of the reaction according to the invention are monohalopropanediol and dialkylamine.
Dialkylamine in the context of the present invention is understood as meaning the lower dialkylamines, preferably dimethylamine and diethylamine. All these compounds are known and commercially available. Said dialkylamines are liquids having a boiling point of 7C (dimethylamine) and 50C (diethylamine) at normal pressure. The particularly preferred dialkylamine is dimethylamine. As is known, halopropanediol exists in two structural forms, in particular as 3-halopropane-1,2-diol or as 2-halopropane-1,3-diol, the first mentioned compound being much the more frequent. The formulae below are intended to illu-strate the two structures, where X i8 a halogen:
f~2-X ~a-~
CH-OH CH-X
l~2 ~ CHa-~
3-halopropane- 2-halopropane-1,2-diol 1,3-diol.
The halopropanediols are also liquids. As chlorine is the usual halogen, 3-chloropropane-1,2-diol, whose boiling under normal pressure is 213C, i8 the preferred com-pound. The dialkylaminopropanediol prepared by the process according to the invention is therefore prefer-ably a dimethylaminopropanediol, in particular 3-dimethylaminopropane-1,2-diol.
The process according to the invention has a number of advantages compared with the prior art. The reaction can be carried out with a substantially higher concentration of dialkylamine or, expressed in another way, with a substantially lower water content. The reaction time is additionally much shorter. A high space-time yield is obtained because of the higher dialkylamine concentration and the shorter reaction time. The chemical yield of dialkylaminopropanediol, relative to glycerol monohalo-hydrin employed, is also very high. As a rule, it is 91to 97%. A further advantage of the process according to the invention is the high purity of the dialkylaminopro-panediol obtained. It can frequently be reused without distillative working up. In a distillative fine purifica-tion, only very little residue is produced. Said advan-tages also result when a crude halopropanediol is used as starting material, i.e. for example a chloropropanediol as is obtained by hydrolysis of epichlorohydrin, in particular without further purification of the hydrolysis product, can rather be employed as such. All these surprising effects of the process according to the invention obviously result from the combination of the 20600~g measures described. The process according to the invention can additionally be carried out batchwise or continuously.
Dialkylaminopropanediol6, such a6 dimethyl- and diethyl-aminopropanediol, are useful intermediates because of their trifunctionality.
The invention will now be illustrated in greater detail by examples.
Example 1 900.0 g (20.0 mol) of dimethylamine and 385.7 g of water (i.e. 30.0% by weight of water, relative to dimethylamine plus water) were initially introduced into a reaction vessel and warmed to 30C with stirring (the following operations were also carried out with stirring; this also applies to all other examples). 734.8 g (6.65 mol) of 3-chloropropane-1,2-diol were continuously added to this mixture in the course of about 2 hours while maintaining a temperature of 30 to 35C. After the addition of chloropropanediol, the mixture was kept at said tempera-ture for a further 7 hours for subsequent reaction, after which all of the chloropropanediol had reacted (the pressure in the reaction vessel, which essentially results from the vapor pressure of the dimethylamine, was 0.15 to 0.20 MPa).
The working up of the reaction product was carried out as follows: the excess dimethylamine and a large part of the water were first removed from the reaction product (contents of the reaction vessel) by distillation at normal pressure and a temperature of at most 115C. The water was further removed by distillation in a water pump vacuum at 0.005 MPa. The mixture of dimethylaminopropane hydrochloride and water then present (about 2% by weight) was treated in the course of one hour with a stoichiomet-ric amount of sodium hydroxide, relative to chloropropanediol employed (i.e. 6.65 mol of NaOH), in the form of an approximately 50% strength by weight solution whilst stirring and maintaining a temperature of at most 50C to release the dimethylaminopropanediol from the hydrochloride. The precipitated salt was removed from the mixture composed of dimethylaminopropanediol, water and precipitated sodium chloride by filtration at room temperature. The filter cake was washed three times with isopropanol (250 ml, 200 ml and 150 ml), after which the individual filtrates were combined. The water and the isopropanol were removed from the mixture of dimethyl-aminopropanediol, water and isopropanol by distillation in a water pump vacuum at a temperature of up to 100C.
The 3-dimethylaminopropane-1,2-diol of boiling point 74 to 75C at 122 Pa was then distilled over. 734.3 g (6.16 mol) of pure product were obtained, i.e. 92.6% of the theoretical yield. The product had a purity of 99.8%.
Example 2 900.0 g (20.0 mol) of dimethylamine and 385.7 g of water (i.e. 30.0% by weight of water, relative to dimethylamine plus water) were initially introduced into a reaction vessel and heated to 40C with stirring. 553.0 g (5.0 mol) of 3-chloropropane-1,2-diol were continuously added to this mixture in the course of approximately 1.5 hours while maintaining a temperature of 40 to 50C.
After the addition of the chloropropanediol, the mixture was kept at said temperature for a further 5 hours for subsequent reaction, after which all of the chloro-propanediol had reacted (the pressure in the reaction vessel was approximately 0.2 NPa). The reaction product was worked up analogously to Example 1. 559.0 g (4.69 mol) of 3-dimethylaminopropane-1,2-diol of boiling point 93C at 0.7 to 0.9 kPa were obtained, i.e. 93.8% of theory. The dimethylaminopropanediol had a purity of 99.5%.
g Example 3 900.0 g (20.0 mol) of dimethylamine, 900.0 g of water (i.e. 50.0% by weight of water, relative to dimethylamine plus water) and 443.0 g (4.0 mol) of 3-chloropropane-1,2-diol were initially introduced into a reaction vesselwith ~tirring and cooling and ad~usted to a temperature of 50 to 55C. The mixture was kept at said temperature for 6 hours with stirring. After this time, all of the chloropropanediol had reacted.
The reaction product was worked up analogously to Example 1. 464.8 g (3.90 mol) of 3-dimethylaminopropane-1,2-diol of boiling point 89C at 0.6 to 0.8 kPa were obtained, i.e. 97.5% of theory. The dimethylaminopropanediol had a purity of 99.5%.
Example 4 443.0 g (4.0 mol) of 3-chloropropane-1,2-diol were initially introduced into a reaction vessel and heated to 40C with stirring. 900.0 g (20.0 mol) of dimethylamine and 1,350.0 g of water (i.e. 60% by weight of water, relative to dimethylamine plus water) were continuously added simultaneously and separately from one another to the heated chloropropanediol in the course of 1 hour while maintaining a temperature of 40 to 45C. After this addition, the mixture was kept at said temperature for a further 4 hours for subsequent reaction, after which all of the chloropropanediol had reacted.
The reaction product was worked up analogously to Example 1. 463.6 g (3.89 mol) of 3-dimethylaminopropane-1,2-diol of boiling point 93C at 0.7 to 0.9 kPa were obtained, i.e. 97.3% of theory. The dimethylaminopropanediol had a purity of 99.5%.
Example 5 443.0 g (4.0 mol) of 3-chloropropane-1,2-diol were initially introduced into a reaction vessel and heated to 35C with stirring. 450.0 g (10.0 mol) of dimethylamine and 675.0 g of water (i.e. 60% by weight of water, relative to dimethylamine plus water) were continuously added simultaneously and separately from one another to the heated chloropropanediol in the course of 1.5 hours while maintaining a temperature of 35 to 40C. After this addition, the mixture was kept at said temperature for a further 5 hours for subsequent reaction, after which all of the chloropropanediol had reacted.
The reaction product was worked up analogously to Example 1. 435.1 g (3.65 mol) of 3-dimethylaminopropane-1,2-diol of boiling point 89C at 0.6 to 0.8 kPa were obtained, i.e. 91.3% of theory. The dimethylaminopropanediol had a purity of 99.5~.
Comparison example (reworking of the example of US Patent 2,147,226) 3.986 kg of a 24.5% strength aqueous dimethylamine solution (i.e. 0.977 kg or 21.71 mol of dimethylamine) and 0.679 kg of a 40% strength aqueous sodium hydroxide solution (i.e. 0.272 kg or 6.80 mol of NaOH) were mixed together in a reaction vessel with stirring and cooling.
Altogether 1.812 kg of glycerol l-monochlorohydrin (i.e.
16.40 mol) were added in 0.091 kg portions in the course of 15 minutes in each case. The reaction mixture was kept at 20 to 40C the whole time. The pressure in the reac-tion vessel rose to 0.1 MPa. The mixture was allowed to stand for 24 hours, after which 0.679 kg of a 40%
strength aqueous sodium hydroxide solution (i.e. 0.272 kg or 6.80 mol of NaOH) were added thereto. The reaction vessel was then opened and the mixture was heated in stages to 105C, the unreacted dimethylamine being removed by distillation. The water was removed from the residual mixture by distillation at a pressure of 6.7 kPa. The distillation residue was cooled to 40C and mixed with 1.520 kg of methanol, whereupon sodium chloride precipitated from the mixture. The salt was removed in a centrifuge, after which the methanol was recovered from the liquid by di~tillation at a pres~ure of 6.7 kPa. 1.295 kg (10.86 mol) of 3-dimethylamino-propane-1,2-diol of boiling point 74 to 75C at 122 Pa were obtained, i.e. 66.3~ of theory.
Claims (3)
1. A process for the preparation of dialkylaminopro-panediol by reaction of monohalopropanediol with excess dialkylamine in the presence of water, which comprises employing the dialkylamine in an amount of at least 2.5 mol per mole of monohalopropanediol and carrying out the reaction in the presence of 25 to 70% by weight of water, relative to the mixture of dialkylamine and water, and at a temperature of 20 to 80°C and recovering the dialkylaminopropanediol from the reaction product.
2. The process as claimed in claim 1, wherein the dialkylamine is employed in an amount of 3 to 6 mol per mole of monohalopropanediol and the reaction is carried out in the presence of 30 to 60% by weight of water and at a temperature of 30 to 60°C.
3. The process as claimed in claim 1 or 2, wherein dimethylamine or diethylamine is employed as the dialkylamine and monochloropropanediol is employed as the monohalopropanediol.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP4102394.3 | 1991-01-28 | ||
| DE4102394A DE4102394A1 (en) | 1991-01-28 | 1991-01-28 | METHOD FOR PRODUCING DIALKYLAMINOPROPANDIOL |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2060049A1 true CA2060049A1 (en) | 1992-07-29 |
Family
ID=6423821
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002060049A Abandoned CA2060049A1 (en) | 1991-01-28 | 1992-01-27 | Process for the preparation of dialkylaminopropanediol |
Country Status (8)
| Country | Link |
|---|---|
| EP (1) | EP0497210B1 (en) |
| JP (1) | JPH04312557A (en) |
| KR (1) | KR100210561B1 (en) |
| BR (1) | BR9200248A (en) |
| CA (1) | CA2060049A1 (en) |
| DE (2) | DE4102394A1 (en) |
| ES (1) | ES2074740T3 (en) |
| MX (1) | MX9200333A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104370757A (en) * | 2014-10-17 | 2015-02-25 | 太仓市茜泾化工有限公司 | Preparation method of 3-dimethylamino-1,2-propanediol |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023184348A1 (en) * | 2022-03-31 | 2023-10-05 | Dow Global Technologies Llc | Water based semi-synthetic metal working fluid composition containing an aminopropanediol |
| CN117447366B (en) * | 2023-10-25 | 2024-04-16 | 广州梵泰新材料科技有限公司 | Antistatic agent and preparation method and application thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2042621A (en) * | 1934-01-16 | 1936-06-02 | Sharples Solvents Corp | Alkylol amines |
| US2147226A (en) * | 1937-02-06 | 1939-02-14 | Dow Chemical Co | Manufacture of 1-dimethylamino-2,3-propanediol |
| NL90665C (en) * | 1953-06-26 | |||
| DE3060177D1 (en) * | 1979-09-10 | 1982-03-11 | Eprova Ag | Process for the preparation of serinol and serinol derivatives |
-
1991
- 1991-01-28 DE DE4102394A patent/DE4102394A1/en not_active Withdrawn
-
1992
- 1992-01-23 ES ES92101077T patent/ES2074740T3/en not_active Expired - Lifetime
- 1992-01-23 EP EP92101077A patent/EP0497210B1/en not_active Expired - Lifetime
- 1992-01-23 DE DE59202472T patent/DE59202472D1/en not_active Expired - Fee Related
- 1992-01-27 BR BR929200248A patent/BR9200248A/en not_active IP Right Cessation
- 1992-01-27 JP JP4012255A patent/JPH04312557A/en not_active Withdrawn
- 1992-01-27 MX MX9200333A patent/MX9200333A/en unknown
- 1992-01-27 CA CA002060049A patent/CA2060049A1/en not_active Abandoned
- 1992-01-28 KR KR1019920001166A patent/KR100210561B1/en not_active IP Right Cessation
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104370757A (en) * | 2014-10-17 | 2015-02-25 | 太仓市茜泾化工有限公司 | Preparation method of 3-dimethylamino-1,2-propanediol |
Also Published As
| Publication number | Publication date |
|---|---|
| MX9200333A (en) | 1992-08-01 |
| ES2074740T3 (en) | 1995-09-16 |
| EP0497210A1 (en) | 1992-08-05 |
| BR9200248A (en) | 1992-10-06 |
| KR100210561B1 (en) | 1999-07-15 |
| KR920014762A (en) | 1992-08-25 |
| DE4102394A1 (en) | 1992-07-30 |
| DE59202472D1 (en) | 1995-07-20 |
| EP0497210B1 (en) | 1995-06-14 |
| JPH04312557A (en) | 1992-11-04 |
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