PL92B1 - Method of replacing amine groups by halogens. - Google Patents
Method of replacing amine groups by halogens. Download PDFInfo
- Publication number
- PL92B1 PL92B1 PL92A PL9219A PL92B1 PL 92 B1 PL92 B1 PL 92B1 PL 92 A PL92 A PL 92A PL 9219 A PL9219 A PL 9219A PL 92 B1 PL92 B1 PL 92B1
- Authority
- PL
- Poland
- Prior art keywords
- nitric acid
- acid
- bromine
- chlorine
- hydrochloric acid
- Prior art date
Links
- 125000003277 amino group Chemical group 0.000 title claims description 6
- 238000000034 method Methods 0.000 title claims description 6
- 229910052736 halogen Inorganic materials 0.000 title 1
- 150000002367 halogens Chemical class 0.000 title 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 11
- 229910017604 nitric acid Inorganic materials 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 claims description 8
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 7
- 239000000460 chlorine Substances 0.000 claims description 7
- 229910052801 chlorine Inorganic materials 0.000 claims description 7
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 6
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052794 bromium Inorganic materials 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 150000001412 amines Chemical class 0.000 claims description 4
- 229910000042 hydrogen bromide Inorganic materials 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical class OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 claims description 3
- ROHFNLRQFUQHCH-YFKPBYRVSA-N L-leucine Chemical class CC(C)C[C@H](N)C(O)=O ROHFNLRQFUQHCH-YFKPBYRVSA-N 0.000 claims description 3
- ROHFNLRQFUQHCH-UHFFFAOYSA-N Leucine Natural products CC(C)CC(N)C(O)=O ROHFNLRQFUQHCH-UHFFFAOYSA-N 0.000 claims description 3
- 235000003704 aspartic acid Nutrition 0.000 claims description 3
- OQFSQFPPLPISGP-UHFFFAOYSA-N beta-carboxyaspartic acid Chemical class OC(=O)C(N)C(C(O)=O)C(O)=O OQFSQFPPLPISGP-UHFFFAOYSA-N 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims 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 claims 1
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical class C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 claims 1
- 235000004279 alanine Nutrition 0.000 claims 1
- 235000001014 amino acid Nutrition 0.000 claims 1
- 150000001413 amino acids Chemical class 0.000 claims 1
- 150000001649 bromium compounds Chemical class 0.000 claims 1
- 150000001805 chlorine compounds Chemical class 0.000 claims 1
- 229910052802 copper Inorganic materials 0.000 claims 1
- 239000010949 copper Substances 0.000 claims 1
- 238000006073 displacement reaction Methods 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 235000005772 leucine Nutrition 0.000 claims 1
- 235000004252 protein component Nutrition 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 230000005484 gravity Effects 0.000 description 5
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
Description
Zaobserwowano, ze grupy aminowe daja sie bezposrednio zastapic chlorem lub bromem, jezeli podzialamy na aminy wroda królewska, a wiec mieszanina kwasu solnego i kwasu azotowego, wzglednie mieszanina bromowodoru i kwasu azoto¬ wego. Nalezy przyjac, ze brom i chlor „in statu nascendi" ruguja grupy aminowe.Ten przebieg reakcji jest nowy i tern wiecej zdumiewajacy, ze stezony kwas azotowy, gdy oddzialywa sam, dziala na aminy, jak wiadomo, inaczej: badz utle¬ niajac, badz tworzac nitroaminy, albo zwiazki wodorotlenowe.Nizej opisany sposób ma te przewage nad dawna metoda zastepowania grup aminowych szeregu tluszczowego przez chlor i brom zapomoca chlorku nitrozytu i bromku nitrozytu, ze reakcja jest bardziej prosta, przebiega szybciej, wydajnosc jest lepsza i odczynniki tansze.PRZYKLADY.Na 50 g leucyny dzialamy 40 cm3 stezonego kwasu solnego (ciezar wlasciwy 1,12) i 40 cm3 stezonego kwasu azotowego (ciezar wlasciwy 1,4) i roztwór ogrzewamy na ka¬ pieli wodnej.Wkrótce nastepuje bardzo silne wydzielanie sie azotu, które po pólgodzinnem ogrzewaniu zazwy¬ czaj ustaje. Wydziela sie przezro¬ czysty olej, skladajacy sie z czy¬ stego prawie kwasu 1-alfa-chloro- isomaslowooctowego (CH3)3. CH. CH2. CHC1. COOH.Znaleziono chlor=23,170/0. Teore¬ tyczna ilosc chloru=23,50°/0- Zwia¬ zek ten jest lewoskretny; zdolnosc skrecania plaszczyzny swiatla spo¬ laryzowanegojest wiec zachowana.60 g leucyny rozpuszczamy w40 cm3 bromowodoru (ciezar wlasciwy 1.4); roztwór ogrzewamy na ka¬ pieli wodnej i dodajemy do niego stopniowo 40 cm8 kwasu azo¬ towego (ciezar wlasciwy 1.49). In¬ tensywne wydzielanie azotu wska¬ zuje ..naiji przebieg reakcji. Gdy wycUielknie ustalo, ochladzamy, przyczem kwas 1 - alfa - bromo- isomaslowooctowy (CH3)2. CH.CH2. CH Br. COOH wydziela sie w postaci oleju. Po jednorazo- wem przedystylowaniu czastkowem w prózni otrzymujemy go w stanie czystym. 5 g kwasu asparaginowego trak¬ tujemy 8 cm3 kwasu solnego (cie¬ zar wlasciwy 1,12) i 8 cm3 kwasu azotowego (ciezar wlasciwy 1,2) i ogrzewamy na kapieli wodnej, a po ustaniu wydzielania sie azo¬ tu ochladzamy, przyczem wydziela sie kwas 1-chlorobursztynowy: C HOOC. CH2. CHC1 COOH wykrystalizowany w stanie czy¬ stym z dobra wydajnoscia. W ana¬ logiczny sposób otrzymujemy kwas 1-bromobursztynowy z kwasu aspa¬ raginowego. Ogrzewanie jest przy- tem zbyteczne. PL PLIt has been observed that the amine groups are directly replaceable with chlorine or bromine if the amines are broken down into aquatic life, a mixture of hydrochloric acid and nitric acid, or a mixture of hydrogen bromide and nitric acid. It must be assumed that bromine and chlorine "in statu nascendi" dislodge the amino groups. This course of reaction is new and more surprising that concentrated nitric acid, when it acts on its own, acts on amines, as is known otherwise: be oxidizing, or Forming nitramines or hydroxyl compounds. The method described below also has an advantage over the old method of replacing the amino groups of the fatty range with chlorine and bromine with the aid of nitrosite chloride and nitrosite bromide, that the reaction is simpler, faster, the yield is better and the reagents are cheaper. 50 g of leucine is treated with 40 cm3 of concentrated hydrochloric acid (specific gravity 1.12) and 40 cm3 of concentrated nitric acid (specific gravity 1.4) and the solution is heated on a water bath. Soon there is a very strong evolution of nitrogen, which after half an hour heating usually ceases, a clear oil is evolved, consisting of almost pure 1-alpha-chloro-isobutyric acetic acid (CH3) 3 CH. CH2. CHCl. COOH. Chlorine = 23 found. , 170/0. Theoretical amount of chlorine = 23.50%. This compound is left-handed; The ability to rotate the plane of polarized light is thus preserved. 60 g of leucine are dissolved in 40 cm3 of hydrogen bromide (specific gravity 1.4); the solution is heated on a water bath and gradually 40 ml of nitric acid are added to it (specific gravity 1.49). The intense evolution of nitrogen indicated that the reaction was proceeding. When it is firmly fixed, cool it down with 1 - alpha - bromo isobutyric acetic acid (CH3) 2. CH.CH2. CH Br. COOH separates as an oil. After one-time partial distillation in vacuum, we get it in a pure state. 5 g of aspartic acid are treated with 8 cm3 of hydrochloric acid (specific weight 1.12) and 8 cm3 of nitric acid (specific gravity 1.2) and heated in a water bath, and after the release of nitrogen has ceased, we cool it and release 1-Chlorosuccinic acid: C HOOC. CH2. CHCl 2 COOH crystallized pure with good yield. In an analogous manner we obtain 1-bromosuccinic acid from aspartic acid. Heating is also superfluous. PL PL
Claims (3)
Publications (1)
| Publication Number | Publication Date |
|---|---|
| PL92B1 true PL92B1 (en) | 1924-05-26 |
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