DD277691A1 - USE OF CARBAMATE LOWER SEKUNDAER ALIPHATIC AMINE AS A SOLVENT AND EXTRACTION AGENT - Google Patents

Abstract

The invention relates to the use of the carbamates of lower secondary aliphatic amines as solvents and extractants. The invention describes the use of solvents and extractants which can be used in the food industry, the pharmaceutical industry, natural product chemistry and similar fields. According to the invention, the title compounds have an indin Tau (30) value between 55 and 60 kcal / mol, an acceptor number AN of 30 * AN * 35 and a donor number DN of DN> 25 for the extraction of organic substances, especially weakly basic and weakly acidic Substances used at relatively low temperature {solvent, extractant, organics, dialkylammonium dialkyl carbamate, acceptor number, donor number, indin Tau (30) value), gentle, food industry, pharmacy, natural product chemistry}

Description

For this 1 page formulas

Field of application of the invention

The invention relates to the use of carbamates lower secondary aliphatic amines of the general formula I, wherein R 'or R ^{2 is} a methyl, ethyl or propyl radical and the sum of the carbon atoms in the radicals R ¹ and R ^{2 is} a maximum of four, as Solvent or extractant for organic substances.

It can be used in the food industry, in the pharmaceutical and chemical industries, in the chemistry of natural products and similar fields.

Characteristic of the known state of the art

It is known that carbon dioxide reacts with secondary amines to give dialkylammonium dialkylcarbamates (U. Petersen: Methods of Organic Chemistry [Houben-Weyl, eds .: H. Hagemannl, Vol. E4 for the 4th ed. Stuttgart, New York, Georg Thieme Verlag 1983,

5. 142). Recently, only their aqueous solutions were investigated, but recently also the pure salts are gaining more attention (UB Mioi, SVRibnikar, Bull. Soc.Chim.Beograd 43 [1978] 603; 725; 44 [1979] 189; Chem.Abstr.90119791136 930.136 931 91 [1979197 539]. The peculiarities of the lower liquid carbamates, especially dimethylammonium dimethyl carbamate, however, received little attention. This represents an oily liquid which is distillable at 60-61 ⁰ C. His technical production (The Lind Oil Company, H. Hennigl, U.S. Pat. I960); Cherr. Abstr. 54 [1960] 12000, 15252) and the use for the separation of aliphatic and aromatic hydrocarbons in petal chemistry (The Pure Oil Company [Invented by LREHutchings], US Pat. Nos. 2915569 [1960] and 2936283 [1960] Chem. Abstr.54 [1960] 8050 and 16813; [invent. GGBernard],

U.S. Pat. 2,954,285 [1960]; Chem. Abstr. 55 [1961] 2079; [Req. H.A. Lindahl], U.S. Pat. No. 2,996,348 [1960]; Chem. Abstr. 55 [1961] 6847; [Req. L. R. E. Hutchings, W. A. Krewer, N.L. Remes], U.S. Patent No. 2,998,376 [1961]; Chem. Abstr. 55 [1961] 19,224). In a recent patent (Union Carbide Corp. [Erf.S. Theodoropulos], EEP 62161 [1981], Chem. Abstr.98 [1983 | 88842]), the preparation of dry ice and dimethvlamin and the use for the production of carboxylic acid dimethylamides from carbonyl chlorides, Anhydrides and -storn described. Uses conditions in the context of the invention are not known.

Object of the invention

The aim of the invention is the prewound of carbamates of lower secondary aliphatic amines as solvents and extractants for organic, particularly weakly acidic and weakly basic substances.

Explanation of the essence of the invention

The object of the invention is the preheating of carbamates of lower secondary aliphatic amines as solvents and extractants on the basis of physicochemical properties which determine the solubility or extraction capacity. It has been found that the carbamates of the general formula I, wherein R ¹ and R ^{2 have} the abovementioned meaning, can find use as solvents or extractants for organic substances. For this an extensive physicochemical characterization was made.

The carbamates I are clear, highly viscous at room temperature liquids whose viscosity decreases sharply with increasing temperature (Example: dimethylammonium dimethylcarbamate density ρ = 1.021 g · cm " ³ at 30 ° C, refractive index no ³⁰ = 1.4501, viscosity 2O ⁰ C: η = 84cP; 50 ° C: n = IS ^ cPJ. The carbamates in normal pressure distilling mTab.U.w, the distillability results from thermal cleavage into the components carbon dioxide and amine and their recombination upon cooling, this being due to a binding enthalpy between carbon dioxide and amine of only 30-40 kJ / mol allows.

Table 1: Constants of the carbamates I

Carbamate I R ² Smelting h boiling point _Δν Η R ¹ me [ ⁰ C] [° Cl [KJ / mol] me et 15-35 60-61 119 me pr + 62 - me et + 70-71 - et 17-33 62-63 110

Carbamate non-crystalline to obtain

Using the example of dimethylammonium dimethylcarbamate, empirical solvent parameters were determined. The most universal and best-known scale has been the E _T (30) value of Reichhardt (C. Reichardt, E. Harbusch-Görnerl, Liebigs Ann. Chem. 1983, 721). This is due to the extraordinarily large solvatochromatic scope of the negatively solvatochromic pyridinium N-phenolate betaine dyes and is characteristic of the Lewis acidity (acceptor strength) and of the non-specific polarity (non-specific interactions).

 From the determined spectroscopic data follows

E _T (30) = 57.2 kcal / mol

according to which dimethyl ammonium dimethyl carbamate is classified in the class of highly structured and highly polar solvents. From the linear correlation between the E _T (30) value and the acceptor numbers (V. Gutmann, Coord. Chem. Rev. 18 [1976] 225) an average value of

AN = 33.3

calculate. An estimation of the donor number (DN) is carried out with nickel-IN.N.N'.N'-tetramethylethylenediamine-acetylacetonato) -tetraphenylboranate (R.W. Soukup, Chem. Us., Zeit 17 [1983] 129,163)

DN> 25

It is surprising and advantageous for the purposes of the invention that dimethylammonium dimethylcarbamate is a solvent having a high donor capacity similar to secondary amines, but in contrast to these also having high acceptability. It thus takes a certain special position among the solvents. It is unlimitedly miscible with the usual solvents (eg ethers, alcohols, esters, halogenated hydrocarbons, aromatics etc.) and to a limited extent with aliphatic hydrocarbons. Long-chain carboxylic acids (palmitic acid), fats (lard), long-chain alcohols (lanette wax), paraffin, caffeine and many other organic substances were readily extracted in a Soxhlet apparatus. In particular, weakly acidic and weakly basic substances proved to be very extractable. The advantage here is the easy and complete removal of the solvent after extraction and the relatively low temperature of the extraction, whereby the method is predestined especially for thermolabile substances. The solubility of inorganic substances (salts) in the carbamates I is significantly better than in non- standard organic solvents, which indicates a high polarity of the carbamates I (for example, in dimethylammonium dimethylcarbamate LiCl 0.75 mol / l, NaCl 0.31 mol / 1, Cl 0.26 mol / l). It should be noted the possibility of reaction of the amino component in extraction of certain classes of substances.

embodiments Example 1:

general extraction:

Dio extraction in a Soxhlet apparatus (poriodiscontinuous extraction) of palmitic acid, lard, lanottic wax and paraffin was complete after a few extraction cycles. Especially fast was the extraction of palmitic acid.

Example 2:

Extraction of Coffoin from Toe in Comparison with Ethanol (L. Gattermann: Dio Praxis der organischen Chemiker, 4O.Aufl., Borlin, Waltor (Ig Gruytor & Co., 1961, p. 354) in a Soxhlot apparatus org Hour extraction time with dimethylammonium dimothylnarbamat otwa two-thirds of Mongo to coffoin from the parallel experiment.

R ¹ HO _v R ¹

X-X

R ² HOR ²

Formula I

7491

Claims (4)

1. Use of carbamates of the general formula I, wherein R ¹ or R ^{2 is} a methyl, ethyl or propyl radical and the sum of the carbon atoms in the radicals R ¹ and R ^{z is} a maximum of four, characterized in that the carbamates of the general formula I with an E _T (30) value of 55 to 60 kcal / mol, an acceptor number of 30 <AN <35 and a donor number of DN> 25 are used as solvent or extractant. 2. Use according to claim 1, characterized in that the carbamates of the general formula I are used as solvent or extractant for organic substances. 3. Use according to claim 1 and 2, characterized in that the carbamates of general formula I are used for the solution or extraction of weakly basic and weakly acidic substances. 4. Use according to claim 1 to 3, characterized in that the carbamates of the general formula I are used as solvents or extractants in pharmaceutical, life or natural products chemistry or similar areas for the extraction of temperature-sensitive substances use.