DE10016812A1 - Preparation of N-alkyl-N-perfluoroacylperfluoroacylamides, used as perfluoroacylating agents, comprises reacting N-alkyl-perfluorocarboxamide with carboxylic anhydride - Google Patents
Preparation of N-alkyl-N-perfluoroacylperfluoroacylamides, used as perfluoroacylating agents, comprises reacting N-alkyl-perfluorocarboxamide with carboxylic anhydrideInfo
- Publication number
- DE10016812A1 DE10016812A1 DE2000116812 DE10016812A DE10016812A1 DE 10016812 A1 DE10016812 A1 DE 10016812A1 DE 2000116812 DE2000116812 DE 2000116812 DE 10016812 A DE10016812 A DE 10016812A DE 10016812 A1 DE10016812 A1 DE 10016812A1
- Authority
- DE
- Germany
- Prior art keywords
- alkyl
- preparation
- perfluoroacylperfluoroacylamides
- formula
- perfluoroacylating
- 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.)
- Withdrawn
Links
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 title claims abstract description 6
- 238000002360 preparation method Methods 0.000 title claims abstract description 6
- 238000000034 method Methods 0.000 claims description 14
- 238000010992 reflux Methods 0.000 claims description 4
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 125000005010 perfluoroalkyl group Chemical group 0.000 abstract description 2
- 101100294106 Caenorhabditis elegans nhr-3 gene Proteins 0.000 abstract 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract 1
- 125000000217 alkyl group Chemical group 0.000 abstract 1
- 229910052799 carbon Inorganic materials 0.000 abstract 1
- 150000001408 amides Chemical class 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- AWGBWLXGUPTXHF-UHFFFAOYSA-N 2,2,2-trifluoro-n-methyl-n-(2,2,2-trifluoroacetyl)acetamide Chemical compound FC(F)(F)C(=O)N(C)C(=O)C(F)(F)F AWGBWLXGUPTXHF-UHFFFAOYSA-N 0.000 description 3
- IQNHBUQSOSYAJU-UHFFFAOYSA-N 2,2,2-trifluoro-n-methylacetamide Chemical compound CNC(=O)C(F)(F)F IQNHBUQSOSYAJU-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 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 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- -1 perfluoro Chemical group 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- QAEDZJGFFMLHHQ-UHFFFAOYSA-N trifluoroacetic anhydride Chemical compound FC(F)(F)C(=O)OC(=O)C(F)(F)F QAEDZJGFFMLHHQ-UHFFFAOYSA-N 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- PNQBEPDZQUOCNY-UHFFFAOYSA-N trifluoroacetyl chloride Chemical compound FC(F)(F)C(Cl)=O PNQBEPDZQUOCNY-UHFFFAOYSA-N 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/02—Preparation of carboxylic acid amides from carboxylic acids or from esters, anhydrides, or halides thereof by reaction with ammonia or amines
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
Die Erfindung bezieht sich auf ein Verfahren zur Her stellung von N-alkylsubstituierten Bis-(perfluoracyl)amiden.The invention relates to a method for manufacturing position of N-alkyl-substituted bis (perfluoroacyl) amides.
N-Methyl-N-trifluoracetyltrifluoracetamid und seine homologen Verbindungen sind als Perfluoracylierungsmittel brauchbar. Die Herstellung von N-Methyl-N-trifluoracetyltri fluoracetamid wird von J. A. Jung, W. S. Durrell und R. D. Dresdner in J. Am. Chem. Soc. 84 (1962), Seiten 2105-2109 beschrieben. Hierzu wird eine Aufschlämmung von Natriumsand in Tetrahydrofuran erzeugt, N-Methyl-trifluoracetamid in einer kleinen Menge Tetrahydrofuran aufgelöst und zur Sus pension des Natriumsands zugegeben. Dann wird Trifluorace tylchlorid zukondensiert, über Nacht gerührt und dann re fluxiert. Die Ausbeute beträgt etwas über 20% der Theorie. Eine alternative Methode, die von den gleichen Autoren an gleicher Stelle beschrieben wird, ist die Umsetzung von N- Methyl-trifluoracetamid, Trifluoracetylchlorid und Pyridin. Hier ist die Ausbeute etwas größer, ca. 27% der Theorie. Diese beiden Verfahren haben den Nachteil, daß sie sehr ge fährlich sind bzw. die Bildung eines Hydrochlorids mit ent sprechenden Entsorgungsproblemen zur Folge haben.N-methyl-N-trifluoroacetyltrifluoroacetamide and its homologous compounds are as perfluoroacylating agents useful. The preparation of N-methyl-N-trifluoroacetyltri fluoracetamide is by J. A. Jung, W. S. Durrell and R. D. Dresdner in J. Am. Chem. Soc. 84 (1962), pages 2105-2109 described. For this, a slurry of sodium sand is used generated in tetrahydrofuran, N-methyl-trifluoroacetamide in a small amount of tetrahydrofuran dissolved and the Sus pension of sodium sand added. Then Trifluorace condensed tylchloride, stirred overnight and then re flows. The yield is a little over 20% of theory. An alternative method by the same authors same place is described, the implementation of N- Methyl trifluoroacetamide, trifluoroacetyl chloride and pyridine. Here the yield is somewhat larger, approx. 27% of theory. These two methods have the disadvantage that they are very ge are dangerous or the formation of a hydrochloride with ent speaking of disposal problems.
Aufgabe der Erfindung ist es, ein verbessertes Herstell verfahren für derartige, N-alkylsubstituierte Bis-(Perfluor acyl)amide anzugeben.The object of the invention is an improved manufacture process for such N-alkyl-substituted bis (perfluoro to specify acyl) amides.
Das erfindungsgemäße Verfahren sieht vor, daß man Ver
bindungen der allgemeinen Formel (I)
[R1C(O)][R2C(O)]NR3
The process according to the invention provides that compounds of the general formula (I)
[R 1 C (O)] [R 2 C (O)] NR 3
herstellt, wobei R1 und R2 gleich oder verschieden sein kön
nen und einen perfluorierten C1-C3-Alkylrest bedeuten und R3
für eine C1-C4-Alkylgruppe steht, durch Umsetzen von N-Alkyl-
Perfluorcarbonsäureamiden der Formel (II)
where R 1 and R 2 may be the same or different and denote a perfluorinated C1-C3 alkyl radical and R 3 represents a C1-C4 alkyl group, by reacting N-alkyl-perfluorocarboxamides of the formula (II)
R1C(O)NHR3,
R 1 C (O) NHR 3 ,
worin R1 und R3 die obige Bedeutung besitzen, mit Carbonsäu
reanhydriden der Formel (III)
wherein R 1 and R 3 have the above meaning, with carboxylic acid anhydrides of the formula (III)
[R2C(O)]2O,
[R 2 C (O)] 2 O,
worin R2 die obengenannte Bedeutung besitzt.wherein R 2 has the meaning given above.
R1 und R2 sind bevorzugt gleich. Hierzu setzt man natür lich ein Amid und ein Säureanhydrid mit gleichen Perfluoral kylgruppen ein. Wünscht man Produkte mit unterschiedlichen Substituenten für R1 und R2, setzt man entsprechend Amide bzw. Carbonsäureanhydride mit den jeweiligen Substituenten ein.R 1 and R 2 are preferably the same. To do this, an amide and an acid anhydride with the same perfluoroalkyl groups are naturally used. If products with different substituents for R 1 and R 2 are desired, amides or carboxylic acid anhydrides with the respective substituents are used accordingly.
R1 und R2 stehen bevorzugt für die Trifluormethylgruppe. R3 bedeutet vorzugsweise Methyl oder Ethyl. Um eine hohe Re aktionsgeschwindigkeit zu erhalten, arbeitet man vorzugsweise bei erhöhter Temperatur und/oder unter erhöhtem Druck, bei spielsweise unter Rückfluß. Zusatz eines Lösungsmittels ist nicht nötig und erfolgt vorzugsweise nicht.R 1 and R 2 preferably represent the trifluoromethyl group. R 3 is preferably methyl or ethyl. In order to obtain a high reaction speed, one preferably works at elevated temperature and / or under elevated pressure, for example under reflux. The addition of a solvent is not necessary and is preferably not carried out.
Die benötigten Amide der Formel (II) können aus den Per fluoralkylcarbonsäureestern und dem Amin NH2R3 hergestellt werden.The required amides of the formula (II) can be prepared from the per fluoroalkyl carboxylic acid esters and the amine NH 2 R 3 .
Die beim erfindungsgemäßen Verfahren anfallenden Verbin dungen sind als Perfluoracylierungsmittel brauchbar. The verb obtained in the method according to the invention Solutions are useful as perfluoroacylating agents.
Die Vorteile des Verfahrens liegen in der Möglichkeit, nicht umgesetzte Ausgangsstoffe auf einem einfachen Weg wie derzuverwenden bzw. das Verfahren kontinuierlich zu betrei ben. Weiterhin fällt als Nebenprodukt lediglich Trifluores sigsäure an, welche gegebenenfalls wieder leicht in ihr Anhy drid überführt werden kann.The advantages of the process are the possibility unreacted raw materials in a simple way like to use or to continuously operate the process ben. Furthermore, only trifluores falls as a by-product acetic acid, which if necessary easily again in her Anhy drid can be transferred.
Das folgende Beispiel soll die Erfindung weiter erläu tern, ohne sie in ihrem Umfang einzuschränken.The following example is intended to explain the invention further ters without restricting their scope.
CF3 CF 3
CONHCH3 CONHCH 3
+ (CF3 + (CF 3
CO)2 CO) 2
O → (CF3 O → (CF 3
CO)2 CO) 2
NCH3 NCH 3
+ CF3 + CF 3
COOH
COOH
In einem 250 ml Dreihalskolben mit Rückflußkühler wurde N-
Methyltrifluoracetamid (12,7 g; 0,1 mol; 127 gmol-1; Fp.
51-53°C; Kp. 156-157°C) bei Raumtemperatur vorgelegt
und Trifluoressigsäureanhydrid (25,2 g; 0,12 mol; 210 gmol-1;
Kp. 40°C) zugetropft. Anschließend wurde die Reaktion unter
starkem Rückfluß gehalten. Nach 5 Tagen waren etwa 50% der
Ausgangsstoffe umgesetzt. Das erhaltene Rohprodukt wurde
feindestillativ gereinigt.
Kp: 118°C
Ausbeute: 7,1 g (0,0318 mol; 223 gmol-1; 31,8% d. Theorie)
1H-NMR:
3,43 ppm (Singulett, CH3)
13C-NMR:
32,31 ppm (Singulett, CH3),
115,64 ppm (Quartett, CF3),
159,91 ppm (Quartett, CO)
19F-NMR:
1-71,93 ppm (Singulett, CF3)N-methyltrifluoroacetamide (12.7 g; 0.1 mol; 127 gmol -1 ; mp. 51-53 ° C; bp. 156-157 ° C) was placed in a 250 ml three-necked flask with reflux condenser at room temperature and trifluoroacetic anhydride (25 , 2 g; 0.12 mol; 210 gmol -1 ; bp. 40 ° C) was added dropwise. The reaction was then held under strong reflux. After 5 days, about 50% of the starting materials had been converted. The crude product obtained was purified by distillation.
Bp: 118 ° C
Yield: 7.1 g (0.0318 mol; 223 gmol -1 ; 31.8% of theory)
1 H-NMR:
3.43 ppm (singlet, CH 3 )
13 C-NMR:
32.31 ppm (singlet, CH 3 ),
115.64 ppm (quartet, CF 3 ),
159.91 ppm (quartet, CO)
19 F-NMR:
1-71.93 ppm (singlet, CF 3 )
Claims (6)
[R1C(O)][R2C(O)]NR3,
wobei R1 und R2 gleich oder verschieden sein können und einen perfluorierten C1-C3-Alkylrest bedeuten und R3 für eine C1- C4-Alkylgruppe steht, durch Umsetzen von N-Alkyl-Perfluorcar bonsäureamiden der Formel (II)
R1C(O)NHR3,
worin R1 und R3 die obige Bedeutung besitzen mit Carbonsäure anhydriden der Formel (III)
[R2C(O)]2O,
worin R2 die obengenannte Bedeutung besitzt.1. Process for the preparation of N-alkyl-N-perfluoroacyl perfluoroacylamides of the formula (I)
[R 1 C (O)] [R 2 C (O)] NR 3 ,
where R 1 and R 2 may be the same or different and represent a perfluorinated C1-C3-alkyl radical and R3 represents a C1-C4-alkyl group, by reacting N-alkyl-perfluorocarboxamides of the formula (II)
R 1 C (O) NHR 3 ,
wherein R 1 and R 3 have the above meaning with carboxylic acid anhydrides of the formula (III)
[R 2 C (O)] 2 O,
wherein R 2 has the meaning given above.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2000116812 DE10016812A1 (en) | 2000-04-05 | 2000-04-05 | Preparation of N-alkyl-N-perfluoroacylperfluoroacylamides, used as perfluoroacylating agents, comprises reacting N-alkyl-perfluorocarboxamide with carboxylic anhydride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2000116812 DE10016812A1 (en) | 2000-04-05 | 2000-04-05 | Preparation of N-alkyl-N-perfluoroacylperfluoroacylamides, used as perfluoroacylating agents, comprises reacting N-alkyl-perfluorocarboxamide with carboxylic anhydride |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE10016812A1 true DE10016812A1 (en) | 2001-10-11 |
Family
ID=7637605
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE2000116812 Withdrawn DE10016812A1 (en) | 2000-04-05 | 2000-04-05 | Preparation of N-alkyl-N-perfluoroacylperfluoroacylamides, used as perfluoroacylating agents, comprises reacting N-alkyl-perfluorocarboxamide with carboxylic anhydride |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE10016812A1 (en) |
-
2000
- 2000-04-05 DE DE2000116812 patent/DE10016812A1/en not_active Withdrawn
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 8139 | Disposal/non-payment of the annual fee |