US2222455A - Process of producing primary delta-alkenyl malonic esters - Google Patents
Process of producing primary delta-alkenyl malonic esters Download PDFInfo
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- US2222455A US2222455A US105823A US10582336A US2222455A US 2222455 A US2222455 A US 2222455A US 105823 A US105823 A US 105823A US 10582336 A US10582336 A US 10582336A US 2222455 A US2222455 A US 2222455A
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- Prior art keywords
- malonic
- primary
- esters
- ester
- alkyl
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- 150000002148 esters Chemical class 0.000 title description 31
- 238000000034 method Methods 0.000 title description 20
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 16
- 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 16
- -1 alkylidene compound Chemical class 0.000 description 16
- 229910052708 sodium Inorganic materials 0.000 description 16
- 239000011734 sodium Substances 0.000 description 16
- 125000000217 alkyl group Chemical group 0.000 description 14
- 125000001118 alkylidene group Chemical group 0.000 description 14
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- 239000012442 inert solvent Substances 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- ODZPKZBBUMBTMG-UHFFFAOYSA-N sodium amide Chemical compound [NH2-].[Na+] ODZPKZBBUMBTMG-UHFFFAOYSA-N 0.000 description 7
- 239000002904 solvent Substances 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 5
- ZIUSEGSNTOUIPT-UHFFFAOYSA-N ethyl 2-cyanoacetate Chemical compound CCOC(=O)CC#N ZIUSEGSNTOUIPT-UHFFFAOYSA-N 0.000 description 5
- 150000001350 alkyl halides Chemical class 0.000 description 4
- 229940100198 alkylating agent Drugs 0.000 description 4
- 239000002168 alkylating agent Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- IYXGSMUGOJNHAZ-UHFFFAOYSA-N Ethyl malonate Chemical compound CCOC(=O)CC(=O)OCC IYXGSMUGOJNHAZ-UHFFFAOYSA-N 0.000 description 3
- 150000008051 alkyl sulfates Chemical class 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- DENRZWYUOJLTMF-UHFFFAOYSA-N diethyl sulfate Chemical compound CCOS(=O)(=O)OCC DENRZWYUOJLTMF-UHFFFAOYSA-N 0.000 description 2
- 229940008406 diethyl sulfate Drugs 0.000 description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 150000003385 sodium Chemical class 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- KIWBPDUYBMNFTB-UHFFFAOYSA-N Ethyl hydrogen sulfate Chemical compound CCOS(O)(=O)=O KIWBPDUYBMNFTB-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical class [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000007656 barbituric acids Chemical class 0.000 description 1
- 150000003842 bromide salts Chemical class 0.000 description 1
- 238000006473 carboxylation reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 150000004694 iodide salts Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- SNVLJLYUUXKWOJ-UHFFFAOYSA-N methylidenecarbene Chemical group C=[C] SNVLJLYUUXKWOJ-UHFFFAOYSA-N 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000002560 nitrile group Chemical group 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
Definitions
- This invention relates to a new process for the production of primary ni-alkenyl alkyl malonic and cyanoacetic esters. It relates more particularly to a process for the conversion of primary alkylidene malonic and cyanoacetic esters into the corresponding alkyl m-alkenyl esters.
- the primary A1alkenyl alkyl malonic esters and cyanoacetic esters are valuable as intermediates for the production of corresponding primary Al-alkenyl alkyl thiobarbituric acids and barbituric acids, and also for the production of unsaturated monobasic acids, which may be prepared by the de-carboxylation of the malonic esters or by the removal of the nitrile group from the cyanoacetic esters.
- the primary alkylidene malonic esters or cyanoacetic esters are alkylated by means of an alkylating agent, such as an alkyl sulfate, halide, or other alkyl salt, in an inert solvent in the presence of metallic sodium.
- an alkylating agent such as an alkyl sulfate, halide, or other alkyl salt
- metallic sodium reacts with the primary alkylidene compound to produce a sodioderivative, which in turn reacts with the alkyl salt, with the elimination of an inorganic sodium salt, and the production of the desired primary Al-alkenyl alkyl ester.
- the double bond uniting the cyanoacetic or the malonic ester radical with the alkylidene radical is shifted to the A1 position in the alkenyl group, so that the alkylidene group is changed to a A1-alkeny1 group, and the alkyl group of the alkylating agent becomes attached to the methylene carbon of the malonic or cyanoacetic ester.
- the reaction is carried out with metallic sodium in an inert solvent, side reactions are minimized, and the reaction proceeds smoothly, and with good yields.
- any available primary alkylidene malonic ester or cyanoacetic ester may be used.
- the primary alkylidene compounds may be prepared advantageously by the condensation of the corresponding aldehydes with malonic ester or cyanoacetic ester in the presence or" a suitable condensing agent, such as a soluble salt, such as piperidene acetate, as described in my copending application Serial No. 105,825, filed October 15, 1936.
- EmampZe.--ll.5 parts of sodium are powdered under Xylene and rinsed into a suitable reaction vessel equipped with a mechanical stirrer, a reflux condenser, and a dropping funnel, with 350 parts of dry ether.
- the vessel is cooled in an 10 ice bath while 107 parts of n-butylidene malonic ester is added, with stirring, over a period of 10 minutes.
- the resulting solution (the sodio derivative of the ester is formed slowly is refluxed for about 6 hours, after which 85 parts 5 of diethyl sulfate are added over a period of 10 minutes, and the refluxing is continued for another 24 hours.
- n-butylidene malonic ester and sodium are used in about equal molar proportions, and the alkylating agent, the diethyl sulfate, is used in an amount somewhat in excess of equal molar proportions.
- the reaction mixture After the reaction mixture has refluxed for about 24 hours, it is acidified with dilute hydrochloric acid, the ethereal layer is removed, and the aqueous layer 25 is extracted with ether. The ethereal layer and extract are combined, and the ether removed by evaporation at reduced pressure. The residue is then shaken for about 24 hours with aqueous ammonia to remove any unalkylated material, and the desired ester is extracted from the ammonia with ether, washed with water, and distilled. The resulting product ethyl nA1-butenyl malonic ester, boils at 104-107 C./2-3 mm.
- the ethyl sulfate used in the above example may be replaced by an equivalent amount of any other alkyl sulfate, or alkyl halide, or other alkyl salts, with the introduction of corresponding alkyl groups into the final product. If alkyl halides are used, it is advantageous to use the bromides or the iodides, as these are somewhat more reactive than the chlorides, and increase the efiiciency of the reaction.
- n-butylidene malonic ester in place of the n-butylidene malonic ester, other primary alkylidene malonic esters, such as n-propylidene, isobutylidene, n-pentylidene, citronellylidene, and other malonic esters may be used as all of the primary alkylidene malonic esters, or aralkylidene malonic esters, react in an analogous manner.
- the primary alkylidene and aralkylidene cyanoacetic esters may be alkylated by a procedure similar to that outlined in the example, with the use of metallic sodium in an inert solvent, and, as an alkylating agent, an alkyl salt, such as an alkyl halide or sulfate.
- an alkyl salt such as an alkyl halide or sulfate.
- solvents which do not react with the sodium or other reactants
- solvents including such solvents as dry ether, benzene, toluene, etc.
- the solvent most advantageous for the production of a given primary A1alkenyl malonic or cyanoacetic ester is the solvent in which the intermediate sodium derivative is the most soluble.
- ether is the best solvent, whereas for others, benzene or toluene may give better results.
- Other inert solvents may also-be used, and particularly solvents in which the intermediate sodium derivatives are relatively soluble.
- Sodamide may be used in place of the metallic sodium, in an inert solvent, with about the same high conversion; but, if sodamide is used, it must be handled with due precautions, as, if not properly handled, it is explosive.
- One way in which it may be used safely involves dissolving it in liquid ammonia, admixing the solution with an inert solvent, such as benzene, ether or the like, and removing the liquid ammonia by vaporization. The inert solvent, containing the sodamide, may then be used in the process.
- esters of primary ni-alkenyl alkyl malonic acids which comprises reacting a primary alkylidene malonic ester with a substance of the class consisting of metallic sodium and sodamide in an inert solvent, and replacing the sodium in the resulting sodio-derivative with an alkyl group by means of an alkyl salt.
- esters of primary ni-alkenyl alkyl malonic acids which comprises reacting an alkyl halide with a primary alkylidene malonio ester in the presence of metallic sodium in an inert solvent.
- esters of primary nl-alkenyl alkyl malonic acids which comprises reacting an alkyl sulfate with a primary alkylidene malonic ester in the presence of metallic sodium in an inert solvent.
- esters of primary nl-alkenyl alkyl malonic acids which comprises reacting an alkyl salt with a primary alkylidene malonic ester in the presence of metallic sodium in an inert solvent.
- A1-all enyl alkyl malonic acids which comprises reacting an alkyl salt with a primary alkylidene malonic ester in the presence of a substance of the class consisting of metallic sodium and sodamide in ether.
- esters of primary ni-alkenyl alkyl malonic acids which comprises reacting an alkyl salt with a primary alkylidene malonic ester in the presence of a substance of the class consisting of metallic sodium and sodamide in benzene.
- esters of primary nl-alkenyl alkyl malonic acids which comprises reacting an alkyl salt with a primary alkylidene malonic ester in the presence of a substance of the class consisting of metallic sodium and sodamide in toluene.
Description
Patented Nov. 19, 1940 UNlTED STATES PATENT OFFME PROCESS OF PRODUCING PRIMARY A1- ALKENYL MALONIC ESTERS Arthur C. Cope, Bryn Mawr,
Incorporated, Philadelphia,
Sharp & Dohme,
Pa., assignor to Pa., a corporation of Maryland '7 Claims.
This invention relates to a new process for the production of primary ni-alkenyl alkyl malonic and cyanoacetic esters. It relates more particularly to a process for the conversion of primary alkylidene malonic and cyanoacetic esters into the corresponding alkyl m-alkenyl esters.
The products which are produced by this novel process, the primary A1alkenyl alkyl malonic esters and cyanoacetic esters, are valuable as intermediates for the production of corresponding primary Al-alkenyl alkyl thiobarbituric acids and barbituric acids, and also for the production of unsaturated monobasic acids, which may be prepared by the de-carboxylation of the malonic esters or by the removal of the nitrile group from the cyanoacetic esters.
In accordance with the process of the present invention, the primary alkylidene malonic esters or cyanoacetic esters are alkylated by means of an alkylating agent, such as an alkyl sulfate, halide, or other alkyl salt, in an inert solvent in the presence of metallic sodium. Apparently the metallic sodium reacts with the primary alkylidene compound to produce a sodioderivative, which in turn reacts with the alkyl salt, with the elimination of an inorganic sodium salt, and the production of the desired primary Al-alkenyl alkyl ester. In the course of the reaction, the double bond uniting the cyanoacetic or the malonic ester radical with the alkylidene radical is shifted to the A1 position in the alkenyl group, so that the alkylidene group is changed to a A1-alkeny1 group, and the alkyl group of the alkylating agent becomes attached to the methylene carbon of the malonic or cyanoacetic ester. As the reaction is carried out with metallic sodium in an inert solvent, side reactions are minimized, and the reaction proceeds smoothly, and with good yields.
In carrying out the process, any available primary alkylidene malonic ester or cyanoacetic ester may be used. The primary alkylidene compounds may be prepared advantageously by the condensation of the corresponding aldehydes with malonic ester or cyanoacetic ester in the presence or" a suitable condensing agent, such as a soluble salt, such as piperidene acetate, as described in my copending application Serial No. 105,825, filed October 15, 1936. Other methods of preparing these primary alkylidene esters may be used, of course, but the process described in my said prior application is of particular advantage, inasmuch as it is applicable to the production of the alkylidene esters from any available aldehyde, and enables a wide range of the primary alkylidene esters to be prepared.
The invention will be further illustrated by the following specific example, but it is not limited thereto. 5
EmampZe.--ll.5 parts of sodium are powdered under Xylene and rinsed into a suitable reaction vessel equipped with a mechanical stirrer, a reflux condenser, and a dropping funnel, with 350 parts of dry ether. The vessel is cooled in an 10 ice bath while 107 parts of n-butylidene malonic ester is added, with stirring, over a period of 10 minutes. The resulting solution (the sodio derivative of the ester is formed slowly is refluxed for about 6 hours, after which 85 parts 5 of diethyl sulfate are added over a period of 10 minutes, and the refluxing is continued for another 24 hours. The n-butylidene malonic ester and sodium are used in about equal molar proportions, and the alkylating agent, the diethyl sulfate, is used in an amount somewhat in excess of equal molar proportions. After the reaction mixture has refluxed for about 24 hours, it is acidified with dilute hydrochloric acid, the ethereal layer is removed, and the aqueous layer 25 is extracted with ether. The ethereal layer and extract are combined, and the ether removed by evaporation at reduced pressure. The residue is then shaken for about 24 hours with aqueous ammonia to remove any unalkylated material, and the desired ester is extracted from the ammonia with ether, washed with water, and distilled. The resulting product ethyl nA1-butenyl malonic ester, boils at 104-107 C./2-3 mm.
The ethyl sulfate used in the above example may be replaced by an equivalent amount of any other alkyl sulfate, or alkyl halide, or other alkyl salts, with the introduction of corresponding alkyl groups into the final product. If alkyl halides are used, it is advantageous to use the bromides or the iodides, as these are somewhat more reactive than the chlorides, and increase the efiiciency of the reaction.
Similarly, in place of the n-butylidene malonic ester, other primary alkylidene malonic esters, such as n-propylidene, isobutylidene, n-pentylidene, citronellylidene, and other malonic esters may be used as all of the primary alkylidene malonic esters, or aralkylidene malonic esters, react in an analogous manner.
The primary alkylidene and aralkylidene cyanoacetic esters may be alkylated by a procedure similar to that outlined in the example, with the use of metallic sodium in an inert solvent, and, as an alkylating agent, an alkyl salt, such as an alkyl halide or sulfate. Some of the primary alkylidene cyanoacetic esters tend to polymerize, in contrast to the corresponding primary alkylidene malonic esters, Which are quite stable. In such cases it is advantageous to employ the more stable alkylidene malom'c esters.
Various inert solvents, i. e., solvents which do not react with the sodium or other reactants, may be used, including such solvents as dry ether, benzene, toluene, etc. In general, the solvent most advantageous for the production of a given primary A1alkenyl malonic or cyanoacetic ester is the solvent in which the intermediate sodium derivative is the most soluble. Thus, for some products, ether is the best solvent, whereas for others, benzene or toluene may give better results. Other inert solvents may also-be used, and particularly solvents in which the intermediate sodium derivatives are relatively soluble.
. Sodamide may be used in place of the metallic sodium, in an inert solvent, with about the same high conversion; but, if sodamide is used, it must be handled with due precautions, as, if not properly handled, it is explosive. One way in which it may be used safely involves dissolving it in liquid ammonia, admixing the solution with an inert solvent, such as benzene, ether or the like, and removing the liquid ammonia by vaporization. The inert solvent, containing the sodamide, may then be used in the process.
Among the primary A1-alkenyl malonic and cyanoacetic esters which may be readily prepared by the process, with good yields, and with aminimum of undesirable side reactions, are the following:
n-Propyl nl-n-propenyl malonic ester Ethyl ni-n-butenyl malonic ester n-Propyl nl-n-butenyl malonic ester Isopropyl A1-n-butenyl malonic ester Allyl ni-n-butenyl malonic ester Ethyl ni-iso-butenyl malonic ester Methyl A1-nheptenyl malonio ester Ethyl isobutenyl cyanoacetic ester Allyl nl-n-butenyl cyanoacetic ester Isopropyl ni-n-butenyl oyanoacetic ester Ethyl nl-n-heptenyl cyano-acetic ester Methyl ni-n-pentenyl cyanoacetic ester It will thus be seen that by the present invention, I provide a novel and advantageous process for the production of primary ni-alkenyl lalkyl malonic esters and cyanoacetic esters, by the .alkylation of the corresponding primary alkylidene malonic or cyanoacetic ester, With'the production of the desired product with high yields and in a condition such that it can be readily purified and isolated.
I claim:
l. The process of preparing esters of primary ni-alkenyl alkyl malonic acids which comprises reacting a primary alkylidene malonic ester with a substance of the class consisting of metallic sodium and sodamide in an inert solvent, and replacing the sodium in the resulting sodio-derivative with an alkyl group by means of an alkyl salt.
2. lhe process of producing esters of primary ni-alkenyl alkyl malonic acids which comprises reacting an alkyl halide with a primary alkylidene malonio ester in the presence of metallic sodium in an inert solvent.
3. The process of producing esters of primary nl-alkenyl alkyl malonic acids which comprises reacting an alkyl sulfate with a primary alkylidene malonic ester in the presence of metallic sodium in an inert solvent.
l. The process of producing esters of primary nl-alkenyl alkyl malonic acids which comprises reacting an alkyl salt with a primary alkylidene malonic ester in the presence of metallic sodium in an inert solvent.
5. The process of A1-all enyl alkyl malonic acids which comprises reacting an alkyl salt with a primary alkylidene malonic ester in the presence of a substance of the class consisting of metallic sodium and sodamide in ether.
6. The process of producing esters of primary ni-alkenyl alkyl malonic acids which comprises reacting an alkyl salt with a primary alkylidene malonic ester in the presence of a substance of the class consisting of metallic sodium and sodamide in benzene.
7. The process of producing esters of primary nl-alkenyl alkyl malonic acids which comprises reacting an alkyl salt with a primary alkylidene malonic ester in the presence of a substance of the class consisting of metallic sodium and sodamide in toluene.
ARTHUR C. COPE.
producing esters of primary
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US105823A US2222455A (en) | 1936-10-15 | 1936-10-15 | Process of producing primary delta-alkenyl malonic esters |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US105823A US2222455A (en) | 1936-10-15 | 1936-10-15 | Process of producing primary delta-alkenyl malonic esters |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2222455A true US2222455A (en) | 1940-11-19 |
Family
ID=22307971
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US105823A Expired - Lifetime US2222455A (en) | 1936-10-15 | 1936-10-15 | Process of producing primary delta-alkenyl malonic esters |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US2222455A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2721201A (en) * | 1955-10-18 | S-monofluoroalkyl barbituric acids | ||
| US2786057A (en) * | 1953-06-05 | 1957-03-19 | American Home Prod | Process of producing 5, 5-di-substituted barbituric acids and product produced thereby |
| US2820035A (en) * | 1953-10-07 | 1958-01-14 | Boehringer Sohn Ingelheim | Barbituric acid derivatives |
-
1936
- 1936-10-15 US US105823A patent/US2222455A/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2721201A (en) * | 1955-10-18 | S-monofluoroalkyl barbituric acids | ||
| US2786057A (en) * | 1953-06-05 | 1957-03-19 | American Home Prod | Process of producing 5, 5-di-substituted barbituric acids and product produced thereby |
| US2820035A (en) * | 1953-10-07 | 1958-01-14 | Boehringer Sohn Ingelheim | Barbituric acid derivatives |
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