US2341663A - Process fob the production of un - Google Patents
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- US2341663A US2341663A US2341663DA US2341663A US 2341663 A US2341663 A US 2341663A US 2341663D A US2341663D A US 2341663DA US 2341663 A US2341663 A US 2341663A
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- United States
- Prior art keywords
- acid
- beta
- acids
- unsaturated
- acrylic acid
- 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
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- 238000000034 method Methods 0.000 title description 26
- 238000004519 manufacturing process Methods 0.000 title description 14
- 239000002253 acid Substances 0.000 description 68
- 150000007513 acids Chemical class 0.000 description 48
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 26
- 150000002148 esters Chemical class 0.000 description 26
- 150000001299 aldehydes Chemical class 0.000 description 14
- 235000019441 ethanol Nutrition 0.000 description 14
- 239000000203 mixture Substances 0.000 description 14
- 230000002378 acidificating Effects 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 12
- 125000004494 ethyl ester group Chemical group 0.000 description 12
- JRXXEXVXTFEBIY-UHFFFAOYSA-N 3-ethoxypropanoic acid Chemical compound CCOCCC(O)=O JRXXEXVXTFEBIY-UHFFFAOYSA-N 0.000 description 10
- HGINCPLSRVDWNT-UHFFFAOYSA-N acrylaldehyde Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 10
- 239000007795 chemical reaction product Substances 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- NDVLTYZPCACLMA-UHFFFAOYSA-N Silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 8
- 238000004821 distillation Methods 0.000 description 8
- 238000005755 formation reaction Methods 0.000 description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- OPXOAENGHZNGBT-UHFFFAOYSA-N 3-ethoxybutanoic acid Chemical compound CCOC(C)CC(O)=O OPXOAENGHZNGBT-UHFFFAOYSA-N 0.000 description 6
- RKSGQXSDRYHVTM-UHFFFAOYSA-N 3-ethoxypropanal Chemical compound CCOCCC=O RKSGQXSDRYHVTM-UHFFFAOYSA-N 0.000 description 6
- -1 aromatic sulfonic acids Chemical class 0.000 description 6
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N benzohydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 239000007800 oxidant agent Substances 0.000 description 6
- 230000001590 oxidative Effects 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-N propionic acid Chemical compound CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 6
- LSNNMFCWUKXFEE-UHFFFAOYSA-N sulfonic acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- KGQIPOITYJJHSU-UHFFFAOYSA-N 3-ethoxypentanoic acid Chemical compound CCOC(CC)CC(O)=O KGQIPOITYJJHSU-UHFFFAOYSA-N 0.000 description 4
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 4
- 229960004838 Phosphoric acid Drugs 0.000 description 4
- 239000003377 acid catalyst Substances 0.000 description 4
- 125000005396 acrylic acid ester group Chemical group 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- 239000000969 carrier Substances 0.000 description 4
- 230000000875 corresponding Effects 0.000 description 4
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 235000011007 phosphoric acid Nutrition 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 239000003638 reducing agent Substances 0.000 description 4
- 229910001923 silver oxide Inorganic materials 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- ZBIAIQCCZGYWSP-UHFFFAOYSA-N 3-ethoxy-2-methylpropanoic acid Chemical compound CCOCC(C)C(O)=O ZBIAIQCCZGYWSP-UHFFFAOYSA-N 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N Allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- SRSXLGNVWSONIS-UHFFFAOYSA-N Benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 2
- FOCAUTSVDIKZOP-UHFFFAOYSA-N Chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N Silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- CMPGARWFYBADJI-UHFFFAOYSA-L Tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000003197 catalytic Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 229910052570 clay Inorganic materials 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 229910001882 dioxygen Inorganic materials 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 230000002140 halogenating Effects 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 125000004435 hydrogen atoms Chemical group [H]* 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000006011 modification reaction Methods 0.000 description 2
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 2
- 150000002763 monocarboxylic acids Chemical class 0.000 description 2
- 235000019260 propionic acid Nutrition 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000010626 work up procedure Methods 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/317—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by splitting-off hydrogen or functional groups; by hydrogenolysis of functional groups
- C07C67/327—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by splitting-off hydrogen or functional groups; by hydrogenolysis of functional groups by elimination of functional groups containing oxygen only in singly bound form
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
- C07C51/377—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by splitting-off hydrogen or functional groups; by hydrogenolysis of functional groups
Definitions
- acrylic acid was produced as those skilled in the art know by brominating allyl alcohol, oxidizing, and adding zinc to split off the bromine, but this too proved far from satisfactory in yield.
- Other complicated methods have been attempted, but none, so far as" I am aware, has been economically and commercially successful in producing these unsaturated acids from aldehydes or from beta-alkoxycarboxylic acids.
- a further object of the invention is to produce alpha,beta-unsaturated acids and esters from unsaturated aldehydes by a process wherein oxygen gas may be used as the oxidizing agent with substantially no formation of polymers or other undesirable products.
- My invention alsohas for its object the production of alpha, beta-unsaturated acids and their esters by heating beta-alkoxycarboxylic acids with an acidic substance.
- My invention also contemplates the production of acrylic acid and esters thereof by treating beta-alkoxypropionic acids with an acid catalyst atlellevated temperatures.
- the present invention also provides a process of producing acrylic acid and the ethyl ester of acrylic acid by treating betaethoxy-propionic acid with an acidic agent at elevated temperatures.
- unsaturated acids are produced from unsaturated aldehydes by reacting unsaturated aldehydes with alcohols to form betaalkoxyaldehydes, oxidizing these beta-alkoxyaldehydes to beta-alkoxycarboxylic acids, and splitting oif alcohol from the thus-formed beta-alkoxycarboxylic acids to leave a double bond.
- beta-alkoxycarboxylic acids from the betaalkoxyaldehydes by the process disclosed in my co-pending application, Ser, No. 272,851, entitled Process for the production of beta-alkoxycarboxylic acids, filed May 10, 1939.
- Unsaturated acids and their esters are produced from betaalkoxycarboxylic acids and. their. esters by subjecting them to elevated temperatures in the presence of an acidic'substance as a cataylst.
- beta-alkoxycarboxylic acids produced in accordance with the process disclosed in my 0- pending application may be heated in the 11 d phase with mineral acids,halogenated fatty acids, or aromatic sulfonic acids, all of which have given good results.
- any beta-alkoxycarboxylic acid or any ester 'of beta-alkoxycarboxylic acids may be employed.
- beta-alkoxypropionic acid beta-methoxypropionic acid ester, betaethoxybutyric acid and its esters, beta-ethoxyalpha-methylpropionic acid, beta-ethoxybutyric acid, beta-ethoxyvaleric acid, beta-ethoxyhydrocinnamic aci and the like.
- acrolein is reacted with ethyl alcohol to form beta-ethoxypropionaldehyde.
- the beta-ethoxypropionaldehyde is then oxidized to beta-ethoxypropionic acid.
- the thus-formed beta-ethoxypropionic acid is heated with toluol sulfonic acid, whereby acrylic acid and its ethyl ester are formed, substantially free of th presence of polymers and others undesirable reaction products. If this latter reaction is carried out in a distillation vessel, the acrylic acid and the ethyl ester thereof formed during the reaction can be distilled oil as they are formed.
- Another method of recovery is first to heat the reaction mixture under reflux and, if desired, under pressure, until the reaction has proceeded sufliciently far, and thereafter to work up the reaction product obtained by distillation. Such distillation may be under reduced pressure, if desired.
- the splitting-on of the ethoxy group may be carried out in the vapor or gas phase. This is accomplished by conducting the beta-alkoxycarboxylic acids over acidic substances impregnated upon,
- Example 1 In accordance with the examples given in my co-pending applications, cited supra, acrolein is used as a starting material and reacted with ethyl alcohol in the presence of water and an acid catalyst, whereby beta-ethoxypropionaldehyde is Heat is applied until distillation products are formed, and at temperatures of about'llo' C. to about C., a liquid mixture is distilled 01!.
- This consists essentially of acrylic acid and acrylic acid ethyl ester, together with a little ethoxypropion'ic acid ethyl ester and unreacted beta-etho'upropionic acid.
- the water formed by the esterlncation of the acid with the split-oi! alcohol will also be present.
- these reaction products are satisfactorily separated from each other, and simultaneously the still unreacted beta-ethoxypropionic acid is subjected to an extensive splitting-oi! of the ethoxy group.
- a process for producing a mixture of acrylic acid and ethyl ester of acrylic acid which comprises mixing about 118 parts of beta-ethoxy propionic acid, about 5 parts of toluol sulfonic acid and about 1 to 2 parts of hydroqulnone to form a liquid mixture, and heating said mixture to a temperature not appreciably higher than the boiling point of acrylic acid until acrylic acid and ethyl ester Of acrylic acid are formed.
- a process for producing a mixture of unsaturated acids and esters thereof from betaalkoxy ,monocarboxylic acids which comprises heating a mixture of beta-alkoxy monocarboxylic acid selected from the group consisting of betaethox propionic acid, beta-ethoxy butyric acid, beta-ethoxy valeric acid, and beta-ethoxy alphamethyl propionic acid a small amount of a reducing agent, and an acidic catalyst selected from the group consisting of benzol sulfoniciacid and toluol sulfonic acid in catalytic amount, in a liquid acid to form an ester thereof, and distilling of! said unsaturated acid and said ester thereof to obtain a distillate containing the said unsaturated monocarboxylic acid and said ester thereof.
Description
Patented Feb. 15, 1944 I PROCESS FOR THE PRODUCTION OF UN- SATURATED ACIDS AND ESTERS Hermann Schulz, Neu-Isenburg, Frankfort-onthe-Main, Germany; vested in the Alien Property Custodian No Drawing. Application May 10, 1939, Serial No. 272,786. In Germany May 19, 1938 2 Claims. (01. 260-486) when unsaturated aldehydes, like. acrolein, were directly oxidized, a very dense reaction product was obtained, accompanied by strong polymerization phenomena, and the desired unsaturated acids occurred only in very small amounts. For this reason special oxidizing agents, such as silver oxide, had to be used if direct oxidation was to be efiective in any measure at all. For example, although it was possible to obtain acrylic acid by direct oxidation of acrolein, or even ofallyl alcohol, the reaction was unsatisfactory in yield and necessarily very costly by reason of the fact that silver oxide had to be employed. The art developed a somewhat cheaper and more convenient method of producing these unsaturated acids by halogenating the corresponding unsaturated alcohols, thereafter oxidizing to form the halogenated acid, and finally removing the halogen to form the unsaturated acid. Thus, for some time, acrylic acid was produced as those skilled in the art know by brominating allyl alcohol, oxidizing, and adding zinc to split off the bromine, but this too proved far from satisfactory in yield. Other complicated methods have been attempted, but none, so far as" I am aware, has been economically and commercially successful in producing these unsaturated acids from aldehydes or from beta-alkoxycarboxylic acids.
It is an object of the present invention to produce unsaturated acids cheaply and conveniently from unsaturated aldehydes without the use of expensive oxidizing agents.
It is another object of the invention to produce unsaturated acids easily and economically from unsaturated aldehydes substantially without the formation of polymers or other undesirable reaction products.
A further object of the invention is to produce alpha,beta-unsaturated acids and esters from unsaturated aldehydes by a process wherein oxygen gas may be used as the oxidizing agent with substantially no formation of polymers or other undesirable products.
My invention alsohas for its object the production of alpha, beta-unsaturated acids and their esters by heating beta-alkoxycarboxylic acids with an acidic substance.
It is also within the contemplation of the invention to produce acrylic acid from acrolein by a simple and inexpensive method.
My invention also contemplates the production of acrylic acid and esters thereof by treating beta-alkoxypropionic acids with an acid catalyst atlellevated temperatures.
rthermore, the present invention also provides a process of producing acrylic acid and the ethyl ester of acrylic acid by treating betaethoxy-propionic acid with an acidic agent at elevated temperatures.
Other objects and advantages of my invention will become apparent from the following description of a preferred procedure for carrying it into practice.
Broadly stated, in carrying the present invention into practice, unsaturated acids are produced from unsaturated aldehydes by reacting unsaturated aldehydes with alcohols to form betaalkoxyaldehydes, oxidizing these beta-alkoxyaldehydes to beta-alkoxycarboxylic acids, and splitting oif alcohol from the thus-formed beta-alkoxycarboxylic acids to leave a double bond. In this three step process, I prefer to produce the beta-alkoxyaldehydes by the process disclosed in my co-pending application, Ser. No. 272,850, entitled Process for the production of beta-alkox'yaldehydes, filed May 10, 1939. 'I also prefer to produce the beta-alkoxycarboxylic acids from the betaalkoxyaldehydes by the process disclosed in my co-pending application, Ser, No. 272,851, entitled Process for the production of beta-alkoxycarboxylic acids, filed May 10, 1939. Unsaturated acids and their esters are produced from betaalkoxycarboxylic acids and. their. esters by subjecting them to elevated temperatures in the presence of an acidic'substance as a cataylst. F r example, beta-alkoxycarboxylic acids produced in accordance with the process disclosed in my 0- pending application may be heated in the 11 d phase with mineral acids,halogenated fatty acids, or aromatic sulfonic acids, all of which have given good results. Thus, sulfuric acid, monochloroacetic acid, phosphoricacid, benzol-sulfonic acid and toluolsulfonic acid have been most successfully employed. Under these conditions, the beta-substituted alkoxy group is split off with the corresponding formation of a double bond in the carbon, tungstic acid or the like. reaction may be carried outat ordinary, elevated or reduced pressures.
amount of a strong reducing agent is of substantial aid in completely avoiding the formation of polymerization products. For this reason, I have found it advantageous to add about 1 to about 2% of hydroquinone, or quinol, to the mixture.
Within the contemplation of the present invention, any beta-alkoxycarboxylic acid or any ester 'of beta-alkoxycarboxylic acids may be employed.
These include, for example, beta-alkoxypropionic acid, beta-methoxypropionic acid ester, betaethoxybutyric acid and its esters, beta-ethoxyalpha-methylpropionic acid, beta-ethoxybutyric acid, beta-ethoxyvaleric acid, beta-ethoxyhydrocinnamic aci and the like.
In. accordance with the general principles of my invention, acrolein is reacted with ethyl alcohol to form beta-ethoxypropionaldehyde. The beta-ethoxypropionaldehyde is then oxidized to beta-ethoxypropionic acid. The thus-formed beta-ethoxypropionic acid is heated with toluol sulfonic acid, whereby acrylic acid and its ethyl ester are formed, substantially free of th presence of polymers and others undesirable reaction products. If this latter reaction is carried out in a distillation vessel, the acrylic acid and the ethyl ester thereof formed during the reaction can be distilled oil as they are formed. Another method of recovery is first to heat the reaction mixture under reflux and, if desired, under pressure, until the reaction has proceeded sufliciently far, and thereafter to work up the reaction product obtained by distillation. Such distillation may be under reduced pressure, if desired.
In a further modification of my invention, the splitting-on of the ethoxy group may be carried out in the vapor or gas phase. This is accomplished by conducting the beta-alkoxycarboxylic acids over acidic substances impregnated upon,
carriers. It has been found that successful results are obtained by using such acidic substances as aluminum metaphosphate, silicic acid, phosphoric acid, sulfuric acid and the like, and these are impregnated upon such carriers as clay, active This gas phase For the. purpose of giving those skilled in the art a better understanding of carrying my invention into practice, the following illustrative example is given:
Example In accordance with the examples given in my co-pending applications, cited supra, acrolein is used as a starting material and reacted with ethyl alcohol in the presence of water and an acid catalyst, whereby beta-ethoxypropionaldehyde is Heat is applied until distillation products are formed, and at temperatures of about'llo' C. to about C., a liquid mixture is distilled 01!. This consists essentially of acrylic acid and acrylic acid ethyl ester, together with a little ethoxypropion'ic acid ethyl ester and unreacted beta-etho'upropionic acid. The water formed by the esterlncation of the acid with the split-oi! alcohol will also be present. Using a small rectification column, these reaction products are satisfactorily separated from each other, and simultaneously the still unreacted beta-ethoxypropionic acid is subjected to an extensive splitting-oi! of the ethoxy group.
Although my invention has been described in connection with .a preferred embodiment, it will be observed that variations may be resorted to and are within the purview of the appended claims. In the foregoing illustrative example, the production of acrylic acid and of acrylic acid ethyl ester was described. Of course, other aphabeta unsaturated acids and esters can be produced by the following reaction and will have the following structural formulae:
are hydrogen atoms or organic radicals.
I claim:
1. A process for producing a mixture of acrylic acid and ethyl ester of acrylic acid which comprises mixing about 118 parts of beta-ethoxy propionic acid, about 5 parts of toluol sulfonic acid and about 1 to 2 parts of hydroqulnone to form a liquid mixture, and heating said mixture to a temperature not appreciably higher than the boiling point of acrylic acid until acrylic acid and ethyl ester Of acrylic acid are formed.
2. A process for producing a mixture of unsaturated acids and esters thereof from betaalkoxy ,monocarboxylic acids which comprises heating a mixture of beta-alkoxy monocarboxylic acid selected from the group consisting of betaethox propionic acid, beta-ethoxy butyric acid, beta-ethoxy valeric acid, and beta-ethoxy alphamethyl propionic acid a small amount of a reducing agent, and an acidic catalyst selected from the group consisting of benzol sulfoniciacid and toluol sulfonic acid in catalytic amount, in a liquid acid to form an ester thereof, and distilling of! said unsaturated acid and said ester thereof to obtain a distillate containing the said unsaturated monocarboxylic acid and said ester thereof.
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2341663A true US2341663A (en) | 1944-02-15 |
Family
ID=3433692
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US2341663D Expired - Lifetime US2341663A (en) | Process fob the production of un |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US2341663A (en) |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2457225A (en) * | 1946-05-01 | 1948-12-28 | Du Pont | Preparation of acrylates |
| US2464768A (en) * | 1946-02-13 | 1949-03-15 | American Cyanamid Co | Preparation of esters of acrylic acid |
| US2469701A (en) * | 1946-02-13 | 1949-05-10 | American Cyanamid Co | Preparation of acrylic acid |
| US2485510A (en) * | 1946-02-13 | 1949-10-18 | American Cyanamid Co | Preparation of acrylic acid and esters thereof |
| US2522366A (en) * | 1947-11-01 | 1950-09-12 | Du Pont | Preparation of substituted glutaric acid esters |
| US2532291A (en) * | 1948-10-02 | 1950-12-05 | Rohm & Haas | Phenylmercaptoacrylates and phenylmercaptomaleates |
| US2649475A (en) * | 1950-06-14 | 1953-08-18 | Distillers Co Yeast Ltd | Process for the manufacture of methyl acrylate |
| US2980730A (en) * | 1957-09-20 | 1961-04-18 | Distillers Co Yeast Ltd | Production of ethyl acrylate |
| DE1124482B (en) * | 1958-06-25 | 1962-03-01 | Wacker Chemie Gmbh | Process for the preparation of acrylic acid esters and ª ‡ -alkylacrylic acid esters by splitting off alcohol from ª ‰ -alkoxymonocarboxylic acid esters |
| DE1124483B (en) * | 1958-06-03 | 1962-03-01 | Wacker Chemie Gmbh | Process for the preparation of acrylic acid and ª ‡ -alkyl acrylic acid esters by splitting off alcohol from ª ‡ - or ª ‰ -alkoxymonocarboxylic acid esters |
| DE1124481B (en) * | 1958-06-03 | 1962-03-01 | Wacker Chemie Gmbh | Process for the preparation of acrylic acid and ª ‡ -alkyl acrylic acid esters by splitting off alcohol from ª ‡ or ª ‰ -alkoxymonocarboxylic acid esters |
| DE1125912B (en) * | 1958-06-03 | 1962-03-22 | Wacker Chemie Gmbh | Process for the preparation of acrylic acid esters and ª ‡ -alkylacrylic acid esters by splitting off alcohol from ª ‰ -alkoxymonocarboxylic acid esters |
| US3115522A (en) * | 1961-07-31 | 1963-12-24 | Shell Oil Co | Production of acrylic acid by the dealkoxylation of beta-alkoxy propionic acid |
| US3341578A (en) * | 1963-10-30 | 1967-09-12 | Air Reduction | Preparation of succinic acid |
-
0
- US US2341663D patent/US2341663A/en not_active Expired - Lifetime
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2464768A (en) * | 1946-02-13 | 1949-03-15 | American Cyanamid Co | Preparation of esters of acrylic acid |
| US2469701A (en) * | 1946-02-13 | 1949-05-10 | American Cyanamid Co | Preparation of acrylic acid |
| US2485510A (en) * | 1946-02-13 | 1949-10-18 | American Cyanamid Co | Preparation of acrylic acid and esters thereof |
| US2457225A (en) * | 1946-05-01 | 1948-12-28 | Du Pont | Preparation of acrylates |
| US2522366A (en) * | 1947-11-01 | 1950-09-12 | Du Pont | Preparation of substituted glutaric acid esters |
| US2532291A (en) * | 1948-10-02 | 1950-12-05 | Rohm & Haas | Phenylmercaptoacrylates and phenylmercaptomaleates |
| US2649475A (en) * | 1950-06-14 | 1953-08-18 | Distillers Co Yeast Ltd | Process for the manufacture of methyl acrylate |
| US2980730A (en) * | 1957-09-20 | 1961-04-18 | Distillers Co Yeast Ltd | Production of ethyl acrylate |
| DE1124483B (en) * | 1958-06-03 | 1962-03-01 | Wacker Chemie Gmbh | Process for the preparation of acrylic acid and ª ‡ -alkyl acrylic acid esters by splitting off alcohol from ª ‡ - or ª ‰ -alkoxymonocarboxylic acid esters |
| DE1124481B (en) * | 1958-06-03 | 1962-03-01 | Wacker Chemie Gmbh | Process for the preparation of acrylic acid and ª ‡ -alkyl acrylic acid esters by splitting off alcohol from ª ‡ or ª ‰ -alkoxymonocarboxylic acid esters |
| DE1125912B (en) * | 1958-06-03 | 1962-03-22 | Wacker Chemie Gmbh | Process for the preparation of acrylic acid esters and ª ‡ -alkylacrylic acid esters by splitting off alcohol from ª ‰ -alkoxymonocarboxylic acid esters |
| DE1124482B (en) * | 1958-06-25 | 1962-03-01 | Wacker Chemie Gmbh | Process for the preparation of acrylic acid esters and ª ‡ -alkylacrylic acid esters by splitting off alcohol from ª ‰ -alkoxymonocarboxylic acid esters |
| US3115522A (en) * | 1961-07-31 | 1963-12-24 | Shell Oil Co | Production of acrylic acid by the dealkoxylation of beta-alkoxy propionic acid |
| US3341578A (en) * | 1963-10-30 | 1967-09-12 | Air Reduction | Preparation of succinic acid |
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