DE1095805B - Process for the preparation of bis-mercaptocarboxylic acid amides - Google Patents
Process for the preparation of bis-mercaptocarboxylic acid amidesInfo
- Publication number
- DE1095805B DE1095805B DEW19326A DEW0019326A DE1095805B DE 1095805 B DE1095805 B DE 1095805B DE W19326 A DEW19326 A DE W19326A DE W0019326 A DEW0019326 A DE W0019326A DE 1095805 B DE1095805 B DE 1095805B
- Authority
- DE
- Germany
- Prior art keywords
- bis
- acid
- preparation
- mercaptocarboxylic acid
- acid amides
- 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.)
- Pending
Links
- 238000000034 method Methods 0.000 title claims description 3
- 238000002360 preparation method Methods 0.000 title claims description 3
- VOWFMWURKUOVSJ-UHFFFAOYSA-N n,n-bis(sulfanyl)formamide Chemical class SN(S)C=O VOWFMWURKUOVSJ-UHFFFAOYSA-N 0.000 title description 2
- 150000003863 ammonium salts Chemical class 0.000 claims description 9
- RSWXSRRFPFDSJS-UHFFFAOYSA-N carbamothioic s-acid Chemical class NC(S)=O.NC(S)=O RSWXSRRFPFDSJS-UHFFFAOYSA-N 0.000 claims description 4
- HDFRDWFLWVCOGP-UHFFFAOYSA-N carbonothioic O,S-acid Chemical class OC(S)=O HDFRDWFLWVCOGP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 14
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- 239000000126 substance Substances 0.000 description 5
- 150000001408 amides Chemical class 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000009835 boiling Methods 0.000 description 3
- GNVMUORYQLCPJZ-UHFFFAOYSA-N carbamothioic s-acid Chemical class NC(S)=O GNVMUORYQLCPJZ-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- PMNLUUOXGOOLSP-UHFFFAOYSA-N 2-mercaptopropanoic acid Chemical compound CC(S)C(O)=O PMNLUUOXGOOLSP-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000001476 alcoholic effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 description 2
- 150000003949 imides Chemical class 0.000 description 2
- -1 monocarboxylic acids form acid amides Chemical class 0.000 description 2
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 2
- SLRXWWRZJVBSIY-UHFFFAOYSA-N 2-sulfanylacetamide Chemical compound C(CS)(=O)N.SCC(=O)N SLRXWWRZJVBSIY-UHFFFAOYSA-N 0.000 description 1
- ZZURXLMHTYYCST-UHFFFAOYSA-N 2-sulfanylacetic acid Chemical compound OC(=O)CS.OC(=O)CS ZZURXLMHTYYCST-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000004848 alkoxyethyl group Chemical group 0.000 description 1
- 238000007098 aminolysis reaction Methods 0.000 description 1
- VXIVSQZSERGHQP-UHFFFAOYSA-N chloroacetamide Chemical compound NC(=O)CCl VXIVSQZSERGHQP-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000002951 depilatory effect Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 238000009950 felting Methods 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- SJKREZXAJDSKQQ-UHFFFAOYSA-N n-propyl-2-sulfanylacetamide Chemical compound CCCNC(=O)CS SJKREZXAJDSKQQ-UHFFFAOYSA-N 0.000 description 1
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical class CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229960002317 succinimide Drugs 0.000 description 1
- 238000009988 textile finishing Methods 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q5/00—Preparations for care of the hair
- A61Q5/04—Preparations for permanent waving or straightening the hair
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/46—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing sulfur
Landscapes
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Birds (AREA)
- Epidemiology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Verfahren zur Herstellung von Bis-mercaptocarbonsäure)-amiden Es ist bekannt, daß Ammoniumsalze von Monocarbonsäuren beim Erhitzen unter Wasserabspaltung Säureamide bilden (vgl. Paul Karrer, »Lehrbuch der organischen Chemie«, 11. Auflage, 1950, S. 253: Die Säureamide sind durch Säuren oder Alkalien zu Carbonsäuren verseifbar (vgl. Paul Karrer, »Lehrbuch der organischen Chemie«, 11. Auflage, 1950, S. 253: Auch substituierte Carbonsäuren können auf diese Weise Axnide bilden (vgl. Paul Karrer, »Lehrbuch der organischen Chemie«, 11. Auflage, 1950, S.262: Eine Bis-(amid)-bildung aus den Ammoniumsalzen der Monocarbonsäuren findet jedoch nicht statt. Substituierte Dicarbonsäuren können ebenfalls Imide bilden (vgl. Zofia Jerzmanowska und Maria ja- Zur Durchführung obiger Reaktionen wendet man wasserabspaltende Mittel an, erhitzt oder destilliert. Ferner kann man auch auf Grund der bekannten Tatsache, daB die Temperatur, bei der Wasser aus einer chemischen Verbindung abgespalten wird, mit sinkendem Lediglich die Ammoniumsalze der Dicarbonsäuren geben unter gleichen Verhältnissen Imide, z. B. Succinimid (vgl. Paul Karrer, »Lehrbuch der organischen Chemie«, 11. Auflage, 1950, S. 316: worska-Krolikowska in »Roczniki Chemii«, 28, S. 397 [1954] Luftdruck herabgesetzt wird, die Umsetzung unter einem geeigneten Vakuum vornehmen.Process for the preparation of bis-mercaptocarboxylic acid amides It is known that ammonium salts of monocarboxylic acids form acid amides when heated with elimination of water (cf. Paul Karrer, "Textbook of Organic Chemistry", 11th edition, 1950, p. 253: The acid amides can be saponified to carboxylic acids with acids or alkalis (cf. Paul Karrer, "Textbook of Organic Chemistry", 11th edition, 1950, p. 253: Substituted carboxylic acids can also form axnides in this way (cf. Paul Karrer, "Textbook of Organic Chemistry", 11th edition, 1950, p.262: However, bis (amide) formation from the ammonium salts of the monocarboxylic acids does not take place. Substituted dicarboxylic acids can also form imides (cf.Zofia Jerzmanowska and Maria ja- To carry out the above reactions, dehydrating agents are used, heated or distilled. Furthermore, on the basis of the known fact that the temperature at which water is split off from a chemical compound, only the ammonium salts of the dicarboxylic acids give imides under the same proportions, e.g. B. Succinimide (cf. Paul Karrer, "Textbook of Organic Chemistry", 11th edition, 1950, p. 316: worska-Krolikowska in "Roczniki Chemii", 28, p. 397 [1954] air pressure is reduced, the implementation below a suitable vacuum.
Es ist auch schon bekannt, Mercaptocarbonsäureamide durch Einwirkung von H,S auf konzentrierte, alkoholische, mit konzentriertem Ammoniak versetzte Lösungen von Halogencarbonsäureamiden zu erhalten. So kann z. B. Thioglykolsäureamid durch Einleiten von H, S in eine konzentrierte, alkoholische, mit etwas konzentriertem Ammoniak versetzte Lösung von Chloracetamid oder aber aus dem Äthylester der Thioglykolsäure und konzentriertem Ammoniak bei gewöhnlicher Temperatur hergestellt werden (vgl. Beilstein, Bd. 111, S.257). Auch wurde schon vorgeschlagen, Thioglykolid mittels Ammoniak in das Amid der Thioglykolsäure zu überführen.It is also already known that mercaptocarboxamides can be obtained by the action of H, S on concentrated, alcoholic solutions of halocarboxamides to which concentrated ammonia has been added. So z. B. thioglycolic acid amide by introducing H, S into a concentrated, alcoholic solution of chloroacetamide mixed with a little concentrated ammonia or from the ethyl ester of thioglycolic acid and concentrated ammonia at ordinary temperature (cf. Beilstein, vol. 111, p.257 ). It has also been proposed to convert thioglycolide into the amide of thioglycolic acid by means of ammonia.
Ferner ist es bekannt, Mercaptocarbonsäureamide durch Aminolyse von Alkoxyäthylestern von Mercaptocarbonsäuren herzustellen (vgl. USA.-Patentschrift Nr. 2714119).It is also known to mercaptocarboxamides by aminolysis of To prepare alkoxyethyl esters of mercaptocarboxylic acids (cf. USA.-Patent No. 2714119).
Schließlich ist es auch bekannt, daß das Ammoniumsalz der Thioglykolsäure bei einer trockenen Destillation Die erfindungsgemäß herstellbaren Bis-(mercaptocarbonsäure)-amide sind bisher in der Literatur noch nicht beschrieben worden und gehören einer neuen Stoffgruppe an.Finally, it is also known that the ammonium salt of thioglycolic acid in a dry distillation The bis (mercaptocarboxylic acid) amides which can be prepared according to the invention have not yet been described in the literature and belong to a new group of substances.
Bis - (mercaptocarbonsäure) - amide hydrolysieren in Wasser unter Bildung von 1 Mol Mercaptocarbonsäure und 1 Mol Mercaptomonocarbonsäureamid.Bis (mercaptocarboxylic acid) amides hydrolyze in water under Formation of 1 mole of mercaptocarboxylic acid and 1 mole of mercaptomonocarboxamide.
Beispiele 1. 30 g des Ammoniumsalzes der Thioglykolsäure werden im Olpumpenvakuum bei etwa 32 bis 40 mm Druck im Claisenkolben im Ölheizbad auf etwa 80 bis 160°C erhitzt. Nacheinander gehen N H, und H20 über. Im Kolben bleibt dann Bis-(thioglykolsäure)-amid, eine kristalline Substanz, mit dem Siedepunkt von 123°C bei 12 mm Druck zurück. Die Ausbeute im Kolbenrückstand beträgt 90 °/o = 21,0 g.EXAMPLES 1. 30 g of the ammonium salt of thioglycolic acid are heated to about 80 to 160 ° C. in an oil pump vacuum at about 32 to 40 mm pressure in a Claisen flask in an oil heating bath. One after the other, NH and H20 pass over. Bis (thioglycolic acid) amide, a crystalline substance with a boiling point of 123 ° C at 12 mm pressure, then remains in the flask. The yield in the flask residue is 90% = 21.0 g.
2. 20 g des n-Propylaminsalzes der Thioglykolsäure werden im Ölpumpenvakuum bei etwa 13 bis 16 mm Druck im Claisenkolben im Ölheizbad auf etwa 80 bis 170°C erhitzt. Der Rückstand bildet Bis-(thioglykolsäure)-n-propylamid mit dem Siedepunkt von 124°C bei 8 mm Druck. Die Ausbeute im Kolbenrückstand beträgt 93 % = 13,0 g.2. 20 g of the n-propylamine salt of thioglycolic acid are placed in an oil pump vacuum at about 13 to 16 mm pressure in the Clais flask in an oil heating bath to about 80 to 170 ° C heated. The residue forms bis (thioglycolic acid) -n-propylamide with the boiling point of 124 ° C at 8 mm pressure. The yield in the flask residue is 93% = 13.0 g.
3. 10 g des Ammoniumsalzes der Thiomilchsäure werden im Ölpumpenvakuum bei etwa 25 mm Druck im Claisenkolben im Ölheizbad auf etwa 80 bis 140'C erhitzt. Der Rückstand bildet Bis-(thiomüchsäure)-Thiodiglykolsäureimid bildet (vgl. Beilstein, 27, S. 249: Es wurde nun überraschenderweise gefunden, daß beim Erhitzen im Vakuum die Ammoniumsalze von Mercaptomonocarbonsäuren Bis-(mercaptocarbonsäure)-amide liefern. Der Reaktionsmechanismus z. B. bei der Mercaptoessigsäure (Thioglykolsäure) ist folgender: amid, eine kristalline Substanz, mit dem Siedepunkt von 115° C bei 25 mm Druck. Die Ausbeute im Kolbenrückstand beträgt 89°/0 = 7,1 g.3. 10 g of the ammonium salt of thiolactic acid are heated in an oil pump vacuum at about 25 mm pressure in a Clais flask in an oil heating bath to about 80 to 140 ° C. The residue forms bis (thiomuchic acid) thiodiglycolic acid imide (cf. Beilstein, 27, p. 249: It has now been found, surprisingly, that the ammonium salts of mercaptomonocarboxylic acids give bis (mercaptocarboxylic acid) amides on heating in vacuo. The reaction mechanism e.g. B. in mercaptoacetic acid (thioglycolic acid) is the following: amide, a crystalline substance, with a boiling point of 115 ° C at 25 mm pressure. The yield in the flask residue is 89 ° / 0 = 7.1 g.
Arbeitet man bei nicht zu hohen Temperaturen, z. B. beim Ammoniumsalz der Thioglykolsäure nicht über 170°C und Luftzutritt, so ist die Ausbeute fast quantitativ, d. h. 90 bis 96 °/o der Theorie. Auf eine Destillation kann auch verzichtet werden.If you work at temperatures that are not too high, e.g. B. the ammonium salt of thioglycolic acid not above 170 ° C and admission of air, the yield is almost quantitative, d. H. 90 to 96 per cent of theory. Distillation can also be dispensed with.
Diese so gewonnenen Stoffe lassen sich vornehmlich für Rohstoffe für keratinerweichende Substanzen verwenden, die in der Textilveredlung (z. B. zum Schrumpffestmachen und Nichtfilzendmachen von Wolle) und in der Kosmetik (z. B. als Dauerwellmittel und Depilatorium) angewendet werden können.These substances obtained in this way can be used primarily for raw materials for Use keratin-softening substances that are used in textile finishing (e.g. to make them shrink-proof and non-felting of wool) and in cosmetics (e.g. as a permanent waving agent and depilatory) can be used.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEW19326A DE1095805B (en) | 1956-06-28 | 1956-06-28 | Process for the preparation of bis-mercaptocarboxylic acid amides |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEW19326A DE1095805B (en) | 1956-06-28 | 1956-06-28 | Process for the preparation of bis-mercaptocarboxylic acid amides |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1095805B true DE1095805B (en) | 1960-12-29 |
Family
ID=7596456
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEW19326A Pending DE1095805B (en) | 1956-06-28 | 1956-06-28 | Process for the preparation of bis-mercaptocarboxylic acid amides |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE1095805B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2868420A1 (en) * | 2004-04-06 | 2005-10-07 | Oreal | USE OF DIMERCAPTOAMIDES FOR PERMANENT DEFORMATION OF KERATIN FIBERS |
| US7875268B2 (en) | 2004-04-06 | 2011-01-25 | L'oreal S.A. | Dimercaptoamides, compositions comprising them as reducing agents, and processes for permanently reshaping keratin fibers therewith |
-
1956
- 1956-06-28 DE DEW19326A patent/DE1095805B/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2868420A1 (en) * | 2004-04-06 | 2005-10-07 | Oreal | USE OF DIMERCAPTOAMIDES FOR PERMANENT DEFORMATION OF KERATIN FIBERS |
| EP1584615A1 (en) * | 2004-04-06 | 2005-10-12 | L'oreal | Use of dimercaptoamides for permanently deforming of keratinic fibres |
| US7875268B2 (en) | 2004-04-06 | 2011-01-25 | L'oreal S.A. | Dimercaptoamides, compositions comprising them as reducing agents, and processes for permanently reshaping keratin fibers therewith |
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