LIQUID AMMONIA RESEARCH in 1938-A REVIEW* GEORGE W. WATT The University of Texas, Austin, Texas AND
NORMAN 0. CAPPEL The Ohio State University, Columbus, Ohio
I
N any field of investigation rather marked changes have found that this substance is diamagnetic in weak in the direction of research effort are frequently dis- magnetic fields (< 300 oersted). It has been suggested cernible. That such changes may occur over rela- that the observed magnetic susceptibility of the comtively short periods of time is demonstrated when one pound may be interpreted as indicating that the reacconsiders studies involving the use of liquid ammonia tion of NO with Na in liquid ammonia involves reducand of solutions in this solvent. No longer than five tion to the NO- ion having the structure, :N::o: . . . . years ago, a majority of such researches had as their objective the study of physical properties of ammonia The dielectric polarization of liquid ammonia (23.8) or of ammonia solutions. More recently, however, the has been found to be less than the polarization of gaseattention of the organic chemist has been attracted by the somewhat unique solvent properties of ammonia. The result has been a rapidly expanding utilization of Amide M.P. this solvent in the preparation and study of reactions **3?3.5'C. LiNa of organic compounds, in the study of the constitu**208' NnNHz **33S0 KN& tionof naturally occurring substances, and in the solution 309' RbNH, of other problems wherein the properties of ammonia 262' CsN& Zn(NHh permit the realization of experimental conditions not obtainable with other solvents. Of more than one hundred publications considered in the following pages, well over two-thirds are primarily concerned with problems in the field of organic ous ammonia (49.6) and less than that of its liquid or chemistry. Over the same period, the results of studies gaseous mono-, di-, and trimethyl derivatives (9). on physical properties of ammonia solutions appeared The examination of the Raman spectra of liquid amonly relatively infrequently although very much re- monia a t -40°, of solutions of NHpNOx2NH3, and of mains to be done in that direction. 2NH4SCN.5NH3has shown the existence of weak lines a t or near 3460 and 3545 cm.? (10). These solutions I. PHYSICOCHEMICAL STUDIES also give Raman lines a t or near 1387, 1456 (attributed Huster and Vo.@ (6)have determined the magnetic to NH,+ or NO.-). (attributed to " ,, 1655 and 1687 em.-' susceptibility of solutions of sodium in liquid am- NH4+): monia as a function of concentration. The results show of lithium, potassium, ~ h atomic , heats of that the magnetic susceptibility of dissolved sodium rubidium, cesium, calcium, strontium, and barium in varies from weak paramagnetism in concentrated solu- liquid ammonia over a range of concentrations have tions to a strong "normal" paramagnetism in dilute been determined by Schmidt and co-workers (11). solutions with the intermediate concentrations being ith hi^^, calcium, strontium, and barium have a nega. diamagnetic. Calculations based on data taken over tive potassium, rubidium, and cesium a zero heat the dilute range show a value of one Bohr magneton solution, for the atomic susceptibility of the sodium atom. The and co.workers (12, 13) have reported the re. diamagnetism found over the intermediate range is as- suits of their on the preparation and physical cribed to the presence of Na2 molecules. When nitric properties of certain of the metal amides. The amides oxide is allowed to react with a solution of sodium in the alkali metals ( ~ iN, ~ K, , ~ b cs) , were prepared liquid ammonia there results a compound the simplest by the interaction of the metals with liquid ammonia in formula for which is NaNO (7). m z e r and Long (8) the presence of a platinum catalyst. Zinc amide was formed by the action of gaseous ammonia on zinc di* For earlier papers in this series see references (1-5). 219
ethyl (method of Frankland) and'cadrnium amide by the interaction of cadmium thiocyanate and potassium amide in liquid ammonia (method of Bohart). Particnlar care was taken to insure the formation of pure amides. In Table 1 the values obtained for various physical constants of the amides thus prepared are summarized. Burgess and Kahler (14) have made a detailed study of the influence of various catalysts upon the rate of reaction between the alkali metals and liquid ammonia a t -33'C. They have found that platinized platinum, rusted iron, nickel, and ferrous oxide were the most efficient catalysts. Sodium amide in solution was shown to exert a poisoning effect upon the catalysts. An account of the study of the system Na-NaC1-NH3 (15) includes tables showing the solubility, specific gravity, and vapor pressure a t 0, - 11, - 15, and -20°C. The solubility of sodium chloride was found to decrease rapidly with an increase in the concentration of sodium. At - 11, - 15, and -20°C., sodium chloride is stable in the form of the ammonate, NaCl.5NH3. Studies on the systems NaC1-NaBr-NH3, NaCl-NaNOs-NH3, NaBr-NH3, andNaN03-NH3 have been made by Portnov and Ravdin (16). The solnbility of NaBr and NaN03 in liquid ammonia was found to decrease with increasing concentration of NaC1. No evidence was obtained for the formation of mixed crystals. The solubility of NaBr was found to increase from 117.6 g. a t -44.5°C. to 1370 g. per 1000 g. NH3 a t -25", that of NaN03from 706 g. a t -50.5 to 1485g. per 1000 g. NH3 a t 60°. A study has been made of the solubility of lithium nitrate in liquid ammonia over the temperatnre range -77.7 to 264.0°C., the specific gravity of solutions a t 20°, the conductivity of saturated solutions from -33 to 20°, and the decomposition voltage of lithium nitrate in liqnid ammonia a t -40°, 0°, and 25' between Pt-Pt and Pt-Ni electrodes (17). The solubility curve indicated the existence of the following ammonates: LiN03.8NH3, 4NH8, and 2NH3. The decomposition potential of lithium nitrate between platinum electrodes was found to decrease from 5 . 2 ~ a. t -40' to 4 . 0 ~ .a t 25'. Shiba and Tanabe (18)have recently determined the rotatory dispersions and the temperatnre coefficients of the specific rotation of d-glucose, d-fructose, sucrose, lactose, and or-methyl-d-glncoside in liquid ammonia. The measnrements were carried out a t wave-lengths ranging from (A), = 0.644 to 0.436 and over the temperature range -35 to -63OC. Graphical representation of the specific rotations showed good agreement with Drude's simple dispersion curve of lactose. The influence of treatment with liquid ammonia on the physical properties of regenerated cellulose has recently been determined (19). I t has been shown that regenerated cellulose may be used for dialysis experiments in ammonia. A theoretical discussion of the electrochemical properties of liquid ammonia, based on numerous mathematical equations, has recently been presented by Makishima (20). The solubility product law was found
to be valid for binary salts in liquid ammonia, and values for the solubility product, heat of solution of gaseous ions, and entropy change during solvation have been deduced for a number of salts. The heat of solvation in liquid ammonia is greater than in water for H+, Ag+, Tl+, Pb++, and halide ions and smaller for the alkali and alkaline-earth ions. The normal potentials of metal and halogen electrodes in liquid ammonia are lower than in water. These effects are attributed to chemical rather than to electrostatic forces. The ionization constant of liquid ammonia a t -34' is about 5 X the theoretical decomposition tension about 0.076~.a t -34', and the normal potential of the nitrogen electrode, - 1 . 5 ~ . From the assumption that the alkali metals in liqnid ammonia form metal ions and solvated electrons, calculations were made for the solubility product, heat of solvation of the electrons, and their entropy change. The value of the heat of solvation of the electron indicates that such solntions should absorb light in the region of 620Ck7200 A.U., which is in accord with the fact that such solutions are indigo blue. These results are in complete agreement with the view that solutions of the alkali metals in liquid ammonia consist of positively charged metal ions and solvated electrons. During electrolysis in liquid ammonia the anode changes may involve the evolution of nitrogen, formation of nitrides or amides, solution of the anode material, evolution of the halogens or oxygen, and electrolytic oxidation; a t the cathode, evolution of hydrogen, deposition of metals, solution of the cathode, formation of an electron solution, and electrolytic reduction. The high overpotential necessary for the formation of hydrogen or nitrogen (approximately 1 . 6 ~a. t the anode and 1 . 2 ~a. t the cathode)-(Pt electrode) permit the occurrence of unusual electrolytic and reduction reactions. The idea has again been advanced that solutions of metals in liquid ammonia consist of colloid particles rather than positively charged metal ionsand solvated electrons. Krnger (21) has shown that values for the absorption coefficient of solutions of sodium in liquid calculated by the theory of Mie for a flattened rotational ellipsoid particle and based on the optical constants of solid metallic sodium are in approximate agreement with absorption measurements of Gibson and Argo. This, together with ultramicroscopic and diffusion experiments, is used to support the conclusion that such solutions are colloidal in character. Freed and Thode (22) have recently criticized the conclusions of Kruger on the basis that the experiments were performed without taking those precautions that are necessary when working with sodium in liquid ammonia. These workers also point out that their work on the magnetic behavior of such solntions is in complete agreement with the accepted view, and also the Fermi-Dirac statistics. Likewise, Huster (23) rejects the concept concerning the colloidal nature of such solutions. 11.
ANALYTICAL METHODS
A method has been developed by Shatenshtein (24) for the titration of solntions in liqnid ammonia a t room
temperature. The apparatus and procedure employed give results which are accurate to *0.2 per cent. and may be applied to solutions in liquefied gases other than ammonia. The solubility of sodium cyanide and sodium chloride and the insolubility of calcium cyanide and calcium chloride in anhydrous liquid ammonia have served as a basis for a proposed method for the analysis of black cyanide melt (25). 111.
INORGANIC REACTIONS
H H H The structure, NH4+ [H:B:N:ii:H] has beeu proH H H posed by Schlesiuger and Burg (26) for the final product of the interaction of diborane and liquid ammonia. This substance reacts with sodium in liquid ammonia a t - 77' to produce one equivalent of hydrogen, thus indicating the presence of one ammonium ion. The slow secondary reaction of the product with liquid ammonia and sodium is explained in terms of a reversible reaction producing NH4BHsNHz. The etherate, (CHa)z0BH3, reacts with sodium and ammonia to yield the salt NaBHsNH2. The action of diborane upon NH4(BH&NH2 has been shown (27) to result in the formation of the compound, B2H7N,with H .. H .. H.. the proposed structure, B :N: B :H. With liquid amH HH
mania, B2H7N forms B2H7N.NHa,which reacts with sodium in liquid ammonia to liberate one equivalent of hydrogen and a solid having the formula NaNHrB2H7N. The reaction between potassium and sulfur in liquid ammonia has been utilized by Gonbeau and co-workers (28) in the preparation of potassium monosulfide. From reactions carried out a t -60 to -30°C., there was obtained a product (85-90 per cent. yield) consisting of KpS (95.5 per cent.), K&03 (2.5 per cent.), KzS03 (1.5 per cent.), S (0.2 per cent.), KZSOa (trace), and KNH2 (trace). The interaction of phosphine and lithium in liquid ammonia a t -80°C. has been shown to result in the formation of an ammonated lithium dihydrogen phosphide (29), PH,
-
+ Li + XNHZ
LiPHv4NHs
+ '/*HD + (r - 4)NHa
The corresponding sodium and potassium compounds (30) have been prepared previously, as have the analogous nitrogen and arsenic compounds (31). Treatment of trimethyllead iodide with sodium in liquid ammonia a t its boiling point has been shown to result in a 7 per cent. yield of hexamethyldilead (CHJaPb-Pb(CH& (32). The utilization of liquid ammonia in the study of intermetallic compounds of the alkali metals has beeu surveyed by Weibke (33) in his extensive review of the preparation and properties of intermctallic compounds. By extracting sodium-zinc, potassium-zinc, and potas-
sium-cadmium alloys with liquid ammonia, Zintl and Haucke (34) have isolated crystalline intermetallic compounds having compositions represented by the formulas, NaZnv, KZnla, and KCd13. Data on the crystal structure of these substances have been provided. Compounds of the composition Li3Sb and LisAs have been prepared (35) by the reaction of antimony and arsenic with lithium in liquid ammonia a t -33O. Under similiar conditions, the reaction of phosphorus with solutions of lithium, sodium, and potassium was incomplete and could not be used for the preparation of Li3P, N%P, and &P. In connection with his studies of the two classes of platinous diacidodiammines, King (36) has investigated their behavior toward liquid ammonia. It was found that liquid ammonia parallelled water in its action on the acid radicals. The cis- and trans-dichloro- and -dinitro-amines were recovered unchanged after treatment with liquid ammonia. Cis-dinitrato-diammino platinum was converted completely into tetramminoplatinous nitrate when dissolved in liquid ammonia.
The displacement of the acid radical was not quite complete in the case of the trans-dinitratodiammine. Evidence obtained by Royen (37) indicates that the hydrides of phosphorus, sulfur, and germanium form salt-like compounds with liquid ammonia. The electrical conductivity of PHI, PlzHe, GeH4, and GezHe in liquid ammonia has heen measured; and the electrolysis a liauid ammonia solution of PHI has been shown to result in'the deposition of a t the anode, probably due to the discharge of the P--- ion. When the amorphous hydride, P12Hs, is dissolved in ammonia, i t is believed that a salt of the type, NH4PHrP, is formed. The apparent molecular weight of this salt, as determined in ammouia by measurements of the vapor pressure lowering, is about 2700. It has been s h a m by Heisig (38) that red mercuric sulfide reacts with ammonium sulfide in liquid ammonia to form a black compound having the formula, (NH4)zSGHgS. The marked insolubility of ammonium sulfate in liquid ammonia a t its boiling point has been utilized by Billman and Audrieth (39) in effecting the quantitative separation of sulfuric acid from its mixtures with nitric, alkalysnlfuric, or alkyl- or aryl-sulfonic acids. Potassium uitrilosulfonate, N(S03K)3.2H20,has beeu found to be only slightly soluble in liquid ammonia (4.0). A study has been made of the corrosive action of liquid ammouia solutions of NHL!l, NH4NOa, and NHISCN on various alloys a t room temperature and over a period of three months (41). Chrome-nickel steels and high chrome steels were found to be resistant to corrosion by solutions of NHaCl and NH,NOa, but readily attacked by solutions of NHaSCN. Copper alloys were readily attacked by all three solutions. Nickel, wrought iron, and steel are also appreciably corroded by solutions of all three ammonium salts.
of
N.
ORGANIC REACTIONS
I . Ammonolytic Reactions The ammonolysis of the ethyl esters of acetic, cyanoacetic, ethoxyacetic, lactic, malonamic, . malonic, mandelic, and phenylacetic acids by liquid ammonia a t O°C. has been studied by Audrieth and Kleinberg (42). The reactions were effected in sealed tubes over twenty-four and forty-eight hour periods both in the presence and absence of ammonium chloride. The yields of acid amides obtained were greatest from reactions of forty-eight hours' duration using ammonium chloride as a catalyst. Qualitatively, the reactivities of the esters studied is the same for ammonolysis as for aqueous alkaline hydrolysis. The influence of the various a-substituents upon the ease of ammonolysis has been determined. It has been shown that the amides of the a-hydroxy acids, mandelic and lactic, may be prepared conveniently in an autoclave a t room temperature by the ammonolysis of the corresponding ethyl esters over a period of twenty-four hours. Under these conditions, the yields of amides (80 and 70 per cent., respectively) were not su5ciently improved by the presence of ammonium chloride to warrant its use as a catalyst. Glycerol, together with mixtures of amides of higher fatty acids, has been produced by the ammonolysis of certain fats and oil (43). Linseed, turnsole, cottonseed, olive, and castor oils and animal fats such as lard, mutton tallow, and beef suet have been found to he ammonolyzed quantitatively. The rate of ammonolysis depends to some extent on the nature of the fat or oil and is in general increased by the utilization of high temperatures, a catalyst such as NH4C1, and an emulsifying agent. The influence of ammonium salts on the ammonolysis of ethyl benzoate by liquid ammonia a t 0 and 25-C. has been studied (44). The conversion of ethyl benzoate to benzamide and ethyl alcohol was found to be a pseudo first-order reaction catalyzed by ammonium salts. The catalytic activity of the salts used increases with concentration in the following order, CHrCO%NH,> NHCI
> NH4Br > NHdlO.
The ammonolysis of the 6-mesyl derivatives of 1,2acetone-3,5-benzalglucosehas been shown to result in the formation of the corresponding 6-amino compound in 85 per cent. yield (45).
CsHs H
c'/ 0 0
HIC
This reaction was carried out in a sealed tube a t room temperature and over a period of three weeks. Under similar conditions, 1,2-acetone-3,5-benzalglucose-6-iodohydrim was dehydrohalogenated by liquid ammonia over a period of ten days. The yield of glucofuranose-5, 6-ene thus obtained was 95 per cent. CsHs
CHa
C \'
CaHs
NHI
H
b!
HrC
CHI
"4
The formation of 8'-diethylaminoethyl 8-aminocrotonate by the ammonolysis of 8'-diethylaminoethyl I 6 L This reaction B-chlorocrotonate has been reoorted f~, was carried out in a sealed tube a t room temperature over a period of many hours. CI
I
+
CHC=CHCO1(CHJlN(CtH~)~ 2NHs NHs
-
I
CHC=CHCO,(CHJ2N(CZH&
+ NHC1
1,l-Dicarbethoxy-l-bromo-3-carbomethoxypropane (47) has been found to be only slightly ammonolyzed by treatment with liquid ammonia (less than 5 per cent.) The ammonolysis of n-dodecyl chloride by liquid ammonia in a sealed tube a t 75-80°C. over a period of 72-90 hours has been shown to result in the formation of a mixture containing 28-33 per cent. of n-dodecylamine and 36-37 per cent. of n-didodecylamine (48). Roberts and Horvitz (49) have made a study of the effect of ammonolyzed foods on the growth of albino rats. It was found that failwe to grow occurred in all cases in which the vitamin B complex was allowed to come in contact with liquid ammonia and that the addition of the unaffected vitamin B complex to the ammonolyzed diet caused the rats to grow more rapidly than the control animals on thenormal diet. It is believed that the deleterious effects are due to the action of liquid ammonia on the vitamin B complex (50). 2. Reactions of Alkali and Alkaline Earth Amides Bergstrom (51)hasshownthatthereactionbetweenthe alkali amides and quinoline or isoquinoline in liquid ammonia a t room temperature probably involves the formation of soluble unstable addition comoounds of the
K
K
In the presence of potassium nitrate, an excess of potassium amide reacts with quinolme to form 2-aminoquinoline and small quantities of Caminoquinoline. In the presence of mercury, potassium amide and quinoline react to form a dilute potassium amalgam and relatively
I l l NH~CHJH-CH-CH-CH-CH -W
HsC
\C/
CH8
"cl 0 ' \o
H
small quantities of 2-aminoquinoline while sodium have been summarized. The preparation of mono- and amide and isoquinoline form sodium amalgam and 1- dialkylacetylenes by the simultaneous reaction between aminoisoquinoline. Barium amide and quinoline react sodium acetylide, sodium amide, and alkyl halides in liqto form the 2-amino compound. The mechanism of uid ammonia has been further studied by Bried and these reactions has been discussed in detail and an Hennion (58). n-Hexyl bromide, when treated with soautoclave suitable for carrying out reactions in liquid dium acetylide and sodium amide in liquid ammonia a t ammonia on a fairly large scale has been described. A -33°C. gave a 38 per cent. yield of dihexylacetylene, number of aminoquinolines have been prepared by while n-octyl bromide gave a 57 per cent. yield of octyltreating substituted quinolines with an excess of potas- acetylene and a 15 per cent. yield of dioctylacetylene. sium amide (in 'the presence of potassium nitrate) or At room temperature, n-octyl bromide gave a 27 per with barium amide (either alone or in the presence of cent. yield of dioctylacetylene and a 15 per cent. yield of barium thiocyanate) in liquid ammonia a t room tem- octylacetylene. Decyl bromide a t room temperature perature over periods of several days (52). The sub- yielded decylacetylene and decylamine. Ruzika and Hofmann (59) have shown that the addistituent groups in 2-quinolinesulfonic acid and 2methoxyquinoline were replaced by the amino group tion of acetylene to the keto group in the 17-position when treated with a liquid ammonia solution of potas- in trans-dehydroandrosterone, sium amide or of potassium amide and potassium nitrate. The presence of the amino group in the 2 position or of the hydroxyl group in the 2 or 8 position prevents the direct introduction of the amino group. On the other hand, the ease of substitution is enhanced by the presence of the carboxyl group in the 2 or 4 posimay be accomplished by adding an ether-benzene solution in the quinoline nucleus. 4-Amino-2-phenyl quinoline has been formed by the tion of the ketone to a solution of potassium acetylide action of potassium amide and potassium nitrate (or in liquid ammonia a t temperatures considerably below mercury) on 2-phenyl-quinoline in liquid ammonia a t the boiling point of ammonia. Removal of ammouia followed by the addition of water and removal of nnroom temperature (53). reacted ketone led to the isolation and identification of A6-17-ethinyl-5-androstene23-trans-17-diol.
The potassium salt is converted to the amino compound by hydrolysis. By reactions similar to those given above or by the use of barium amide alone, amino derivatives of 6- and gphenyl- and 7,s- and 5,6-benzoquinolines have been prepared. When potassium amide is used in the absence of potassium nitrate or mercury, G-phenyl- and 8-phenyl-quinolines are converted to tars while 7,s-beuzo- and 5,G-benzo-quinolines yield 25-35 per cent. of the corresponding amino derivatives. Cope and Hancock have recently described a method for the preparation of alkyl derivatives of ethyl isopropylidene malonate (54) and ethyl (I-methylpropylidene)-malonate (55). It was found that the sodium derivatives of these substances (conveniently prepared by reaction with sodium amide in liquid ammonia) could be readily alkylated in an inert solvent by the ordinary alkylation agents. On the other hand, an attempt to prepare the sodium derivatives of alkylidenecyanoacetic esters by reaction with sodium amide in liquid ammonia resulted in the cleavage and polymerization of the cyanoacetic esters (56). 3. Reactions of Solutions of Metals Reactions of sodium acetylide: Improvements in the procedure for the formation of sodium acetylide from acetylene and sodium in liquid ammonia a t its boiling point have been described (57) and the results of the use of this salt in the preparation of substituted acetylenes
In an analogous manner, trans-androsterone was converted to 17-ethinylandrostane-3-trans-17-diol. By means of essentially the same experimental procedure, Inhoffen and co-workers (60) have prepared 17-ethinylestra-3,17-diol from estrin and potassium acetylide:
Similarly, equilin has been converted to 17-ethinyldihydroequilin and equilenin to 17-ethinyldihydroequilenin. Campbell and co-workers (61) have shown that sodium acetylide in liquid ammonia will condense with many aldehydes and ketones to give acetylenic carbinols together with smaller amounts of the corresponding glycols. The yield of the carbinols was increased and that of the glycols decreased by passing acetylene gas into the mixture during the course of the reaction. The following mechanism has been suggested to explain the course of these reactions,
resulted in a methoxyl content of 45 per cent. and a yield of 0.2 per cent. of tetramethyl glucose on hydrolysis. When the methylation of cellulose is camed out exI/ 0 clusively in liquid ammonia a t -70°C. (67), a methoxyl content of 45.6 per cent. is realized only after repeated treatment with sodium and methyl iodide. Measurement of the viscosity of choloform solutions of the various methylation products obtaiued in this stepwise methylation process showed that the decreased viscosity referred to above is first observed when a methoxyl content of 42 per cent. is reached. This procedure involving exclusive methylation in ammonia has also been applied to the methylation of starch (68, 69). A total of five successive treatments with sodium and methyl iodide resulted in a methoxyl content of 45.5 per cent. The methylation of amylose (45.5 per cent. OCHa) and amylopectin (45.9 per cent. OCHd has also been reported. he application of these methods is not limited to It is believed that this method has certain advantages the introduction of the methyl group into organic moleover the usual methods for the preparation of this type cules. Reactions discussed in the following paragraphs of compound. Sodium acetylides (prepared in liquid illustrate their usefulness in the introduction of ethyl ammonia) have been shown to be relatively unreactive and benzyl groups as well. toward acetals in various solvents (62). The earlier synthetic methods developed by du Alkylation: Earlier papers in this series (2-5) have Vigneaud and co-workers have beeu used to advantage referred to the use of liquid ammonia in connection with in the preparation of amino acids containing deuterium the methylation of saccharides. The procedure em- (70). Methionine-p,y-dz has been obtained in 78 per ployed usually involves the addition of a partially cent. yield by tbe reduction of S-benzylhomocysteinemethylated material to a solution of sodium in liquid p , y 4 with sodium in liquid ammonia followed by the ammonia a t low temperatures. The ammonia is then addition of methyl iodide to the reduction product. removed from the resulting sodium salt and the latter CsH5CH2X!HDCHDCH(NHdC0OH Na treated with methyl iodide in an organic solvent. With salt formation being effectedat a temperatureof -80°C., Hess and Lung (63) have shown that methylraffinose containing 44.1 per cent. OCHa may be further methylated by the above method to an average methoxyl con- Similarly, homocystine-@,pr,y,y'-drwas prepared in tent of 51.3 per cent. (Calcd., 51.8 per cent.). Anisole 90 per cent. yield by the reduction of S-benzylhomowas used as the medium for the reaction between the cysteine-p,y-dzwith sodium in liquid ammonia followed sodium salt and methyl iodide. Recent experiments on by oxidation, the methylation of the Schardinger dextrins have also CsHsCH1SCHDCHDCH(NH2)COOH Na been described (64). HnO NaSCHDCHDCH(NH,)COONa That the last step in the methylation process may be [O] [HOOCCH(NH2)CHDCHD]Sn carried out in ammonia as well as in orpanic solvents has also been demonstrated. Thus, by-treating partially premethylated sugars with sodium in liquid am- Each compound was found to contain the theoretical monia followed by direct addition of methyl iodide, amount of deuterium. The reaction of pentaerythritol with sodium and Hendricks and Rundle (65) have prepared the tetraethyl bromide in liquid ammonia (71) has been shown methyl derivatives of a-d-glucose, a-d-galactose, and to result in a mixture of the di-, tri- and tetraethyl a-d-mannose. A number of studies reported by Freudenberg and ethers. A satisfactory yield of the diethyl ether was obco-workers show that premethylation prior to treatment tained by the action of sodium and ethyl alcohol in with sodium and methyl iodide in liquid ammonia is liquid ammonia on the dibromohydrin of pentaerynot necessary. Pure unbleached cellulose, methylated thritol. S-Ethylhomocysteine (ethionine) has beeu prepared to a methoxyl content of 4 4 per cent. with dimethyl in 75 per cent. yields from S-benzylhomocysteine by sulfate and yielding 0.05 per cent. of tetramethyl glureduction with a slight excess of sodium in liquid amcose on hydrolysis, has been shown to undergo a marked change when treated with sodium in liquid ammonia monia followed by treatment with ethyl bromide (72), (66). Solutions of the product are much less viscous than solutions of the original material. Further methylation of this product with sodium and methyl iodide HC=CNa 4- R-C-R'
-
+
+
-
+
-
-4
In connection with their studies on the thiolactone of homocysteine (a protein fragment) du Vigneaud and co-workers (73) have prepared the dibenzyl derivatives of both the optical isomers of the diketopiperazine of homocysteine by the action of sodium in liquid ammonia a t -33' on homocysteine diketopiperazine, followed by the addition of benzyl chloride:
The polymer-like substance obtained from d-homocysteine thiolactone hydrochloride by treatment with dilute alkali was also shown to yield the diketopiperazine derivative of S-benzyl-d-homocysteine by reduction with sodium in liquid ammonia followed by benzylation. Similarly, the polymer obtained from 1-homocysteine diketopiperazine by hydrogen peroxide oxidation gave the diketopiperazine derivative of Sbenzyl-Lhomocysteine, thus indicating that the polymerized substance is either a dimeric or polymeric disulfide of homocysteine. Other reactions involving reduction.-The N-methyl derivative of cysteine has been prepared in 40 per cent. yield by the reduction of di-p-toluenesulfonyl-di-Nmethyl cystine by means of a solution of sodium (seven to eight atoms) in liquid ammonia (74).
It was found that an excess of sodium (ten to eleven atoms) during the reduction causes racemization. The reduction of a number of aromatic hydrocarbons by means of calcium hexammonate and ammonia a t room temperature has been reported (75). The reduction of benzene yielded cyclohexene and traces of 1,3cyclohexadiene. Cyclohexene was produced in high yields by the reduction of 1,3-cyclohexadiene while toluene and naphthalene gave the corresponding tetrahydro derivatives. It is of considerable interest to compare these results with the earlier observations of Wooster and Godfrey (76) and with other results obtained in the study of the reduction of aromatic hydrocarbons in liquid ammonia (77).
Gilman and Bradley (78) have studied the reductionof a number of dibenzofuran compounds with sodium in liquid ammonia. Dibenzofuran was reduced to 1,4-dihydrodibenzofuran, and Phydroxydibenzofuran to 1,4dihydro-6-hydroxydibenzofuran. A 26 per cent. yield of dihydrodibenzofuran was obtained by the reduction of 4-methoxydibenzofuran. 3-Aminodibeuzofuran, 3diethylaminodibenzofuran, and 4-aminodibenzofuran upon reduction yielded humus-like materials with 75 per cent. of the amines being recovered unchanged. Calcium in liquid ammonia was found to reduce dibenzofuran to a greater extent than sodium; however, the stage of reduction was not as specific since the product obtained using calcium was found to be a mixture. 1,4-Dihydrodibenzothiophene has been formed by the reduction of dibenzothiophene with an excess of sodium in liquid ammonia followed by the addition of solid ammonium nitrate (79). Studies on the cleavage (80) of 4,4-disubstituted diphenyl ethers by sodium in liquid ammonia have shown that the linkage between oxygen and the phenyl group is strengthened against cleavage by the presence of the following groups, listed according to increasing effectiveness: 9-CHa, pC(CH3)3, p-OCH,, p-NH*. 2,6-Dimethyl-3,5-octadiene has been prepared by the reduction of alloijcimene with sodium in liquid ammonia followed by isolation and catalytic hydrogenation of the reduction product (81). Freudenberg and co-workers (82) have found that lignin undergoes partial demethylation when treated with a solution of potassium amide in liquid ammonia a t 20°C. Under similar conditions, the action of potassium in liquid ammonia results in more extensive demethylation and a t the same time produces more farreaching changes in the character of the lignin. Spruce wood meal is acted upon by sodium in liquid ammonia a t its boiling point. Abont one-half of the product of this action is soluble in aqueous alkali and the soluble fraction includes about two-thirds of the lignin content of the original sample of wood. Under the same experimental conditions the action of sodium amide is markedly less vigorous. An attempt to remove the carbobenzyloxy residue from glucosidocarbobenzyloxytyrosylglobulin with sodium in liquid ammonia met with failure due to the insolubility of the parent substance in ammonia (83). A study has recently been made (84) of the digestibility (by trypsin) of a number of proteins after treatment with sodium in liquid ammonia. It was found that the digestibilities of egg albumin, silk fibroin, and wool are increased. The digestibility of casein is decreased, and that of peptone is unaffected by this treatment. Controls treated only with liquid ammonia appeared to digest as rapidly as the reduced materials. 4. Other Organic Reactions Smith and Adkins (85) have shown that ammonia adds to mesityl oxide to give good yields of diacetoneamine,
(CHJ2C:CHCOCHs
+ NHs
-
(CH&CNH2CH2COCHs
The reaction was effected in a sealed tube a t 10-23'C. over a period of three days. The amides of d- and 1-erythronic acids have been prepared in quantitative yields by the action of liquid ammonia a t room temperature on the corresponding lactones (86). d-a,u-Galaoctonic amide has been formed by the action of liquid ammonia on the lactone of d-a,a-galaoctonic acid (87). 2,4,6,-Trimethyl-6gluconolactone and 3,4,6-trimethyl-6-altronolactone have been converted into the corresponding amides by solution in liquid ammonia a t -33°C. (88). Hilbert and Pinck (89) have shown that fluoryljdene dimethylsulfide rearranges in liquid ammonia to fluorene-1-dimethylsulfide.
A copolymer derived from an equimolecular mixture of 1-pentene and 10-hendecenoicacid when treated with liquid ammonia gave only one cyclic disulfone of the type which would result from a polymer in which one molecule of 10-hendecenoic acid and one molecule of 1-pentene are joined by a sulfone linkage.
COOH
I
CHs (CH& I
I
-CHCH2S02CHCHS*
I
-
COOH I
CH-CHz SO2 /
\SO* \CH-CH, /
I
(~H.)z
The copolymer prepared from sulfur dioxide and a mixture containing five moles of 1-pentene to one mole of 10-hendecenoic acid when treated with liquid ammonia gave two products: one identical with the product obThe reaction between chasmanthin (bitter principles tained from pure 1-pentene polysulfone, the other of calumbo roots) and liquid ammonia over a period of identical with the product obtained from the copolymer containing equimolecular amounts of 1-pentene and 10six hours a t 70% has been shown to lead to the formahendecenoic acid. The results show that the copolytion of the isomeric isochasmanthin (90). Calumbii merization of equimolecular amounts of 1-pentene and similarly treated over a period of twenty-four hours re10-hendecenoic acid with sulfur dioxide proceeds sulted in a mixture of nitrogen-free compounds. through a mechanism which gives a polymeric molecule Marvel and co-workers (91) have continued their of a definite type. Recent work has shown (92) that studies on the degradation of polysulfones by liquid vinyl chloride and vinyl bromide polysulfones, unlike ammonia to cyclic polysulfones and have obtained evithe polysulfones of other olefins, are converted into dence for the copolymerization of olefins with sulfur nitrogen-containing polymers by treatment with liquid dioxide. It has been shown previously that liquid ammonia converts 1-pentenepolysulfoneto a cyclic disul- ammonia. Wooster and co-workers (93) have shown that the fone which is alkali soluble. reaction of triphenylmethylsodium with an excess of ethylene oxide in liquid ammonia a t -33' leads to the formation of a product which, upon hydrolysis, yields r,r,r-triphenylpropyl alcohol. Sodium triphenylmethide was prepared by the action of sodium in liquid ammonia on triphenylchloromethane. Liquid ammonia has been used in the study of the hydrolysis products of 2-benzoylaminofuran (94).
The polysulfone derived from 10-hendecenoicacid when treated with liquid ammonia was also shown to give an alkali-soluble cyclic disulfone. COOH I
( 6 ~ ~ ) . COOH
COOH
I
CH-CHn
/ -CHCH~SOnCH2CHSOs-
\
CH-CHs
I
(pd1 I
COOH
\ so* /
v. PATENTS* In earlier papers in this series, numerous patent references have been overlooked or have been omitted because of lack of sufficientlydetailed information. In the present paper, reference is made to a number of such patents which have been issued within the period covered by these reviews. Processes for the production of urea (95) from carbon dioxide and liquid ammonia involve the formation of ammonium carbamate and its subsequent conversion to urea either in the liquid state or in solution in liquid ammonia. Aminonitriles have been produced by treating glycolic acid nitrile (96), hydroxy'The authors wish to express their thanks to Dr. L. F. Audrieth of The University of Illinois for his coiiperation in supplying a number of these patent references.
nitriles (97),or a mixture consisting of an aldehyde and hydrogen cyanide (98) with liquid ammonia under pressure and a t temperatures not greatly above room temperature. Amino acids (99) such as a-amino-caproic acid may be prepared by the action of liquid ammonia on the corresponding a-halogeno acids. Amino acids have been separated from their mixtures with inorganic salts by extracting the acids in liquid ammonia and leaving behind the ammonia-insolublesalts (100). The preparation of acyl-substituted carboxylic acid amides has been accomplished by means of the interaction of esters of y-methylenecarboxylic acids and substituted alkali metal amides (101). Thus monomethacrylylformamide was formed by adding sodium to a solution of methyl methacrylate and formamide in liquid ammonia. The formation of etbynylcarbinols has been accomplished through the use of liquid ammonia solutions of sodium acetylide a t temperatures below the normal boiling point of ammonia. Thus, in reaction with sodium acetylide, acetone yields dimethylethyuylcarbinol (102); acetaldehyde yields methylethynylcarbinol (103); and ethylene oxide yields 8-ethynylethanol (104). Similarly, the interaction of sodium acetylide and aliphatic y-keto-carboxylic acids leads to the formation of y-ethynyl-y-lactones (105). A method for the production of diiodoacetylene involves the reaction of calcium carbide with a solution of iodine in liquid ammonia a t -34°C. under pressure a t higher temperatures (106). Numerous applications of liquid ammonia in the solution of problems related to the petroleum industry have been patented. These patents are concerned with the selective extraction of olefins from hydrocarbon mixtures (107), the separation of phenols and pyridic basesfrom hydrocarbons (108)in mixtures obtained from various tars and oils, and the extraction of sulfur compounds (109) from crude or distilled oils. In a similar fashion, liquid ammonia has been shown to be suitable for the extraction of phenols, elemental sulfur, sulfonic acids. and other organic sulfur com~oundsin the refindisulfides ing of mineral oil 6 1 0 ) . ~mmonia~insoluble are reduced to soluble mercaptans by reduction in liquid ammonia by the action of ammonium sulfide, cyanides, hydroxylamiue, hydrazine, and so forth, in the presence of ammonium salts, alkali metal amides, or cyanides. In treating the products of the distillation or cracking of petroleum, fractions consisting of middle oils have been separated into portions of different hydrogen content by the solvent action of liquid ammonia (111) or other suitable solvent. Products suitable for use as motor fuels have been formed by extracting bituminous materials such as coal with liquid ammonia (112). The ammonia-soluble substances are subsequently isolated and subjected to cracking temperatures. Liquid ammonia solutions containing an aliphatic diamine such as ethylenediamine and a pyridine or quinoline compound have been used for the removal of carbon deposits (113). A continuous extraction apparatus suitable for use
in the purification of cmde anthracene has been patented (114). Impurities are extracted by means of liquid ammonia under a pressure of one hundred to two hundred pounds per square inch; the resulting solution is continuously removed from the extractor and the ammonia is recovered. Cellulose materials containing esterifiable hydroxyl groups have been converted to an alkali cellulose product by treatment with sodium in liquid ammonia (115), the resulting salts being suitable for use in the preparation of cellulose ethers or esters. Textile materials such as yarns have been converted to products which contain combined nitrogen by treatment with liquid ammonia under pressure (116). The affinity of these products for acid dyes is much greater than that of the untreated materials. Ammonia has been used as a solvent for fibroin derived from degummed natural silk (117). \ , In the production of fertilizers, liquid ammonia has been utilized to introduce combined ammonia (4-6.5 per cent.) into superphosphates (118), and to prepare fertilizer mixtures containing superphosphate and sodium nitrate (119), and calcium cyanamide and calcium nitrate (120). Salts suitable for use as fertilizers have been extracted from kainite, carnallite, or nitrous earth by the solvent action of liquid ammonia (121). Solutions of ammonium nitrate in liquid ammonia have been patented under the claim that such compositions may be transported more safely than either of the constituents alone (122). Metallic sodium has been produced by the electrolysis of liquid ammonia solutions of sodium chloride (123). Both alkali and alkaline earth metals have been purified by taking advantage of the solubility of these metals in liquid ammonia (124). This purification process is, of course, effective only in the separation of the metals from impurities which are insoluble in ammonia. Liquid ammonia has been used to extract sodium cyanide produced by heating sodium with crude calcium cyanamide (125), and in the preparation of colloidal sols consisting of hydroxides of trivalent metals such as iron, aluminum, and chromium (126). It is claimed in another patent that anhydrous salts such as sodium sulfate and calcium chloride may be produced by removing the water of crystallization by treatment with liquid ammonia (127). Application of this treatment is disclaimed in the case of salts which are appreciably soluble in ammonia and in the case of magnesium chloride, the dehydration of which has been reported previously (128). A patent has been issued covering a f i e extinguishing grenade which contains carbon tetrachloride and liquid ammonia (129). The purpose of the latter is to counteract the toxic effects of the carbon tetrachloride vapors.
The writers wish to acknowledge their indebtedness to Professor W. C. Fernelius of The Ohio State Uni-
versity and t o Mr. W. R. Stemen of t h e editorial staff of Chemical Abstracts for their continuing interest in these
reviews, as evidenced by numerous helpful suggestions a n d studied criticism.
LITERATURE CITED
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~
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BRAUER, G. AND E. ZINTL,Z. physik. Chem., B37, 323-52 1937). KING,H.J. S., J. C h . Soc., 1938 (Sept.), 133846. ROYEN,P., Z. anorp. allgem. Chem., 235, 324-36 (Mar., 1938). Hsrsrc, G. B., J . Am. Chem. Soc., 60, 359-61 (Feb., 19'38). BILLMAN. J. H. AND L. F. AUDRIETH, i b d . 60, 1945-6 (Aug., 1938). SISLER,H. AND L. F. AUDRIETH, ibid., 60, 1947 (Aug., 1 Q3.m
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L. S. KEYSER, 5. Am. C h . Soc.. 60,
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.D E. M. -
3A"a i.m u",
~
~
-
HANCOCK, ibid., 60, 2901-2 (Dec.,
(56) COPE,A. C. AND E. M. HANCOCK, ibid., 60, 290'3-6 (Dec., 1938). (57) HENNION,G. F., PIOC.Indiana Acad Sci., 47, 116-21 ,l"lQ\
I'""",.
(58) BRIED,E. A. AND G. F. HENNION, J . Am. Chem. Soc., 60, 1717-9 (Aug., 1938). ,,n??\ L. AND K. HOPMANN, H&. Chim. Acta, 20, 1280-2 (59) RUZIKA, ,'".YC,.
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~
~
0.R., U. S.Pat. 2,106,182; (104) KREIMEIER, 2547 (1938). E R., R , U. S. Pat. 2,122,719; (105) K R E ~ ~ ~ I0. 6669 (1938). (106) VAUGHN, T. H., U. S.Pat. 2,124,218; 7058 (1938). (107) DEANESLY, R. M., U.S. Pal. 1,893,733;
C h . Abstr., 32, Ckenz. Abstr., 32, Chem. Abstr., 32, C h . Abrtr., 27,
It,,",
,
\-pw.
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~~~.~~.
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~
A. H., U. S. Pat. 2,052,722; Chem. Abstr., 30, (114) RADASCH, 7321 (1936). (115) Brit. Pat. 463,056; Chm. Abst.. 31, 6003 (1937). (116) DREYPUS, H., Brit. Pat. 486,305; Chem. Abdr., 32, 8160 l l-Q-R-X-\,. (117) GAJEWSKI, F., H. FINK, E. ROSSNER,AND H. MAHN, U. S.Pat. 1,966,756; C h . Abstr., 28, 5684 (1934). (118) HARVEY,E. W., Can. Pat. 357,412; Chem. Abrtr., 30,4265 \
- --
11QXfi\ ,. \
(119) HARVEY, E. W., U. S.Pat. 2,023,199; C h . Abrtr., 30, 805 (1936). (120) CARO.N. AND A. R. FRANK,Ger. Pat. 611,206; Chm. Abstr., 29, 4126 (1935). (121) KIRCHER,C., F. M ~ ~ L L EAND R , H. SUSSENGDIH,Ger. Pot. 575,914; C h . Abstr., 27, 4871 (1933). (122) FAZEL,C. S., Can. Pat. 356,902; C h . Abrtr., 30, 3603 I,A""",. lORfi\ (123) HARA,R. AND S.:ABE, U.S. Pat. 2,102,151; C h . Abrtr., 32, 1190 (1938). (124) VAUGHN, T. H., U. S. Pat. 2,123,617: Chem. Abstr., 32,
,.""",.
a919 (1 019) "uL-
(125) PRANKE,E. J., U. S. Pat. 1,905,304; Chem. Abrtr., 27, 3567 (1933). (126) Brit. Pal. 441,206; Chm. Abstr., 30, 4587 (1936). (127) JANECKE. E., F. FROWEIN, AND H. G.GnRrzN~n.Ger. Pat. 578.285; Chem. Abstr.. 27, 4359 (1933). (128) Reference 3, p. 234. (129) PLAYaAIR, A. F. AND G. W. F. BRISBIN,Bvit. Pat. 471,831; Chem. Abstr., 32, 1368 (1938).
