US2022182A - Preparation of ethylene oxide - Google Patents
Preparation of ethylene oxide Download PDFInfo
- Publication number
- US2022182A US2022182A US725316A US72531634A US2022182A US 2022182 A US2022182 A US 2022182A US 725316 A US725316 A US 725316A US 72531634 A US72531634 A US 72531634A US 2022182 A US2022182 A US 2022182A
- Authority
- US
- United States
- Prior art keywords
- ethylene oxide
- reaction
- chloroethylacetate
- beta
- hydroxide
- 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.)
- Expired - Lifetime
Links
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 title description 19
- 238000002360 preparation method Methods 0.000 title description 12
- VIRWKAJWTKAIMA-UHFFFAOYSA-N 2-chloroethyl acetate Chemical compound CC(=O)OCCCl VIRWKAJWTKAIMA-UHFFFAOYSA-N 0.000 description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000002585 base Substances 0.000 description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 11
- 239000011541 reaction mixture Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000005325 alkali earth metal hydroxides Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 229940093499 ethyl acetate Drugs 0.000 description 1
- 235000019439 ethyl acetate Nutrition 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/22—Synthesis of the oxirane ring by oxidation of saturated compounds with air or molecular oxygen
Definitions
- the base is gradually added to the beta-chloroethylacetate, while vigorously agitating the reaction mixture, and maintaining it at a temperature between about 40 and about 150 C.
- the concentration of the aqueous base may be varied between wide limits, e. g. from as low as 10 per cent thereof up to or per cent by weight, the choice of concentration being largely a matter of convenienceand economy.
- the following examples show the results obtained by carrying out the reaction between beta-chloroethylacetate and an alkali metal or alkaline earth metal base at varying temperatures and with different concentrations thereof.
- Table I I Percent Reaction Timem yield of mm gag? minutes ethylene 15 oxide EzwmplcZ
- Table II shows the yield of ethyl- 25 ene oxide obtained during a series of runs carried out as above wherein the temperature was held constant at (3., but the concentration of sodium hydroxide ,was varied.
- Example 3 We have carried out the preparation of ethylene oxide using 1.1 moles of calcium hydroxide as the base, obtaining a yield of 74.6 per cent of theoretical based on 9'72 per cent of the beta-chloro- 45 ethylacetate reacted.
- Example 4 We have also carried out the preparation of ethylene oxide at a temperature of 100 C., using 60 1.1 moles of sodium carbonate in a 25 per cent aqueous solution as the base, to obtain a yield of 60.4 per cent of theoretical based on the betachloroethylacetate reacted.
- the step which consists in gradually adding the hydroxide to the beta-chloroethylacetate, While agitating thereaction mixture and maintaining it at a temperature between about 40 and about 150 C.
- the step which consists in gradually adding the hydroxide to the beta-chloroethylacetate, in the molar ratio of about two moles of hydroxide per mole of the presence of a material excess of unreacted beta-chloroethylacetate, while agitating the reaction mixture and maintaining it at a temperature between about 40 and about 150 C.
- the step which consists in gradually adding the hydroxide' to the beta-chloroethylacetate, in the molar ratio of about one mole of hydroxide per mole of beta-chloroethylacetate, While agitating 10 the reaction mixture and maintaining it at a temperature between about 40 and about 150 C.
- the step 15 which consists in gradually adding the hydroxide to -the beta-chloroethylacetate, in the molar ratio of about two moles of hydroxide per mole of beta-chloroethylacetate, while agitating between about 40 and 150 C.
- the step which consists in gradually adding the hydroxide to the beta-chloroethylacetate, in the molar ratio of 35 about two moles of hydroxide per mole of betachloroethylacetate, while agitating the reaction mixtureand' maintaining it at a temperature of about 100 C. a r
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
V Patented Nov. 26, 1935 I 2,022,182 PREPARATION 0F ETHYLENE oxnm Edgar C. Britten, Gerald H. Coleman, and Byron Mate, Midland,'Mich., assignors to The Dow Chemical Company, Midland, Mich., a corporation of Michigan No Drawing. Application May 12, 1934,
Serial No. 725,316
8 Claims. (c1. 260 -54) The present invention regards an improvement in methods for the preparation of ethylene oxide. I
We have found that the reaction between betachloroethylacetate and an alkali metal hydroxide produces either ethylene oxide or glycol, or both i in varying proportions. The proportions of these two compounds in theproduct from the foregoing reaction varies widely, depending upon the conditions in which the reaction is carried out. Moreover, the reaction may be very rapid, particularly in the presence of an excess of the hydroxide, and the highreaction velocity makes it very diflicult to control the course of the reaction so as to produce a good yield of ethylene oxide. The yield of ethylene oxide is also affected by the concentration of the metal hydroxide.
We have now found that, under certain conditions, the formation of glycol is materially suppressed and the reaction proceeds chiefly to the formation of ethylene oxide. It is, therefore, an object of this invention to provide suitable conditions under which the reaction between betachloroethylacetate and a base, such as an alkali metal or alkaline earth metal hydroxide or carbonate, can be carried out to produce a maximum yield of ethylene oxide while avoiding substantially the formation of glycol.
To the accomplishment of the foregoing and related ends, we have now found that the difficulties and uncertainties formerly encountered in producing a good yield of ethylene oxide by the aforesaid reaction are avoided if the base is gradually added to the beta-chloroethylacetate, while vigorously agitating the reaction mixture, and maintaining it at a temperature between about 40 and about 150 C. In this manner we at all times avoid the presence of an excess of unreacted base in the reaction mixture. Then, by such procedure the reaction is made practically independent of the concentration of base employed. Thus, the concentration of the aqueous base may be varied between wide limits, e. g. from as low as 10 per cent thereof up to or per cent by weight, the choice of concentration being largely a matter of convenienceand economy. The following examples show the results obtained by carrying out the reaction between beta-chloroethylacetate and an alkali metal or alkaline earth metal base at varying temperatures and with different concentrations thereof.
tate was placed in a round-bottom flask provided with a stirrer and a reflux condenser. The flask was then heated to and maintained at the various temperatures shown-in the following Table I while 2.2 moles of sodium hydroxide in a 20 per cent aqueous solution was gradually added thereto 5 over the periods of time shown. The reaction mixture was vigorously stirred throughout the reaction period. The yield of ethylene oxide is in per cent of theoretical based on the beta-chloroethylacetate reacted,'which' was in all cases above 10 95 percent.
Table I I Percent Reaction Timem yield of mm gag? minutes ethylene 15 oxide EzwmplcZ The following Table II shows the yield of ethyl- 25 ene oxide obtained during a series of runs carried out as above wherein the temperature was held constant at (3., but the concentration of sodium hydroxide ,was varied.
Table II 30 C(1tiicentfra- T Perlcienif;
on 0 me in me 0 Run sodium minutes ethylene hydroxide oxide 40 Example 3 We have carried out the preparation of ethylene oxide using 1.1 moles of calcium hydroxide as the base, obtaining a yield of 74.6 per cent of theoretical based on 9'72 per cent of the beta-chloro- 45 ethylacetate reacted.
Example 4 We have also carried out the preparation of ethylene oxide at a temperature of 100 C., using 60 1.1 moles of sodium carbonate in a 25 per cent aqueous solution as the base, to obtain a yield of 60.4 per cent of theoretical based on the betachloroethylacetate reacted.
It is a feature of our improved method that 55 ea-"manual chloroethylacetate was gradually added to a 40 per cent aqueous sodium hydroxide solution at a temperature of about C., the yield of ethylene oxide was only 2.7 per cent, the chief-product being ethylene glycol. j
It is readily apparent from the foregoing description of our invention that our improved method for the preparation of ethylene oxide provides a procedure capable of producing high yields of the desired compound without the formation of large proportions of undesirable products, particularly glycol. 1 r
Other modes of applying the principle of our invention may be employed-instead of those explained, change being made as regards the process herein disclosed, provided the step or steps stated by any of the following claims or the equivalent of such stated step or steps be employed. V I
We therefore particularly point out and dis-, tinctly claim as our invention:--- r 1. In carrying out the preparation of ethylene oxide from beta-chloroethylacetate by reaction thereof with a base, the step which consists in gradually adding the base to the beta-chloroethylacetate, while agitating the reactionmixture and maintaining it at a temperature between about 40 and about C.
2. In carrying out the preparationof ethylene oxide from beta-chloroethylacetate by reaction thereof with a hydroxide of an alkali forming metal, the step which consists in gradually adding the hydroxide to the beta-chloroethylacetate, While agitating thereaction mixture and maintaining it at a temperature between about 40 and about 150 C.
3. In carrying out the preparation of ethylene oxide from beta-chloroethylacetate by reaction thereof with an alkali metal hydroxide, the step which consists in gradually adding the hydroxide to the beta-chloroethylacetate, in the molar ratio of about two moles of hydroxide per mole of the presence of a material excess of unreacted beta-chloroethylacetate, while agitating the reaction mixture and maintaining it at a temperature between about 40 and about 150 C.
4. In carrying out the preparation of ethylene oxide from beta-chloroethylacetate by reaction 5 thereof with an alkali earth metal hydroxide, the step which consists in gradually adding the hydroxide' to the beta-chloroethylacetate, in the molar ratio of about one mole of hydroxide per mole of beta-chloroethylacetate, While agitating 10 the reaction mixture and maintaining it at a temperature between about 40 and about 150 C.
5. In carrying out the preparation of ethylene oxide from beta-chloroethylacetate by reaction thereof with an alkali metal hydroxide, the step 15 which consists in gradually adding the hydroxide to -the beta-chloroethylacetate, in the molar ratio of about two moles of hydroxide per mole of beta-chloroethylacetate, while agitating between about 40 and 150 C. 30
7. In carrying out the preparation of ethylene oxide from beta-chloroethylacetate by reaction thereof with sodium hydroxide, the step which consists in gradually adding the hydroxide to the beta-chloroethylacetate, in the molar ratio of 35 about two moles of hydroxide per mole of betachloroethylacetate, while agitating the reaction mixtureand' maintaining it at a temperature of about 100 C. a r
' 8. In carrying out the preparation of ethylene 40' oxide from beta-chloroethylacetate by reaction thereof with an aqueous solution of a base, the step which consists in gradually adding the aque- Ous solution of the base to the beta-chloroethylacetate, while agitating the reaction mixture and 45 maintaining it at a, temperature between about 40 and about 150 C.
EDGAR C. BRITTON.
GERALD H. COLEMAN.
BYRON MATE. 50
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US725316A US2022182A (en) | 1934-05-12 | 1934-05-12 | Preparation of ethylene oxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US725316A US2022182A (en) | 1934-05-12 | 1934-05-12 | Preparation of ethylene oxide |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2022182A true US2022182A (en) | 1935-11-26 |
Family
ID=24914047
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US725316A Expired - Lifetime US2022182A (en) | 1934-05-12 | 1934-05-12 | Preparation of ethylene oxide |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US2022182A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4568759A (en) * | 1984-03-08 | 1986-02-04 | The Dow Chemical Company | Preparation of epoxides |
-
1934
- 1934-05-12 US US725316A patent/US2022182A/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4568759A (en) * | 1984-03-08 | 1986-02-04 | The Dow Chemical Company | Preparation of epoxides |
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