LIQUID AMMONIA RESEARCH GEORGE W. WATT The University of Texas, Austin, Texas AND
NORMAN 0. CAPPEL The Ohio State University, Columbus, Ohio
T
HE publications which have appeared in this field of investigation during the past year cover an unusually wide variety of unrelated subjects. An attempt has been made to classify the various studies in a manner which will render certain topics more readily available to the reader whose interests are specific. In doing this, however, numerous difficulties were encountered and it is recognized that the classification of certain items covered in this review is somewhat arbitrary. I.
PHYSICOCHEMICAL STUDIES,
Ritchey and Hunt (7) have determined the vapor pressure difference, a t 25'C., between pure liquid ammonia and liquid ammonia solutions of ammonium chloride ranging in molality from 0.0051 to 0.900. The densities of the solutions over the range of concentrations studied were also determined. These data have been used as the basis for calculation of activity co&cients for ammonium chloride in liquid ammonia. This information, togethyr with the earlier results of Yost and co-workers (8, 9), has been used to calculate certain standard electrode po&ntials. As applied to the activity coefficientsof ammonium chloride in liquid ammonia, the Debye-Hiickel theory had been found to hold only a t very low concentretions. Kikuti (10) has described studies of the specific gravities of liquid ammonia solutions of ammonium chloride, sodium cbloride, and mixtures of these two salts. The measure, ments for the individual salts were carried out over the temperature range, -30' to 70°C. and from zero concentration to saturation. Plank and Hunt (11) have determined the viscosity of liquid ammonia. The values reported, together with the corresponding values for the density of liquid ammonia, are given in Table 1. TABLE 1 Tcm#nolurc
Dcnsily
"C.
dcc.
1
Vircodly
(or., d c m .
For earlier papers in this series see references (1-5)
SIC.)
A comparison of these values with the data from an earlier investigation indicates that the temperature coefficient of viscosity for ammonia is much smaller than that for any other known liquid. Values for the viscosity a t (20°C.) of liquid ammonia-water mixtures ranging from 0 to 80 per cent. Hz0 have been reported (lla). A maximum viscosity a t 71-2 per cent. Hz0 corresponds to NHaxHz0, where x = 2 or 3. The influenceof iouicsize on solubility and solvation in the systems (KI, KCI, KBr, KN0a)-NH3 and [Mg(NO&, Ca(NOs)i, Sr(NOs)z, Ba(NOs)z]-NH3 has been studied over the temperature range -50' to 50°C. (12). It was found that the solubility of the potassium halides in liquid ammonia increases with increasing anionic radius. The solubility of zinc nitrate (13) has been found to increase from 20.11 g./100 g. NHs a t -77' to 33.62 g,at -3g0, to decrease to 29.01 g. a t 0°, and then increase to 85.40 g. a t 125'. Zinc nitrate was found to form ammonates containing 10 (-75°to-550), 8(-55' to 0°),6 (0' to 5S0),aud4 (above 5S0)molesof NH Jmole of salt. The solubility of cadmium nitrate was found to decrease from 29.5 g./lOO g: NH3 a t - 76' to 0.28 g. a t 37". Sigetomi (14) has &died the binary system NaNH2-NH3 and the ternary system NaNHn-NaCINH3 over the temperature range -20' to 20°C. Values for the solubility of sodium amide in liquid ammonia are given in Table 2. The solubility of sodium amide and of sodium chloride was found to increase rapidly upon addition of sodium chloride or sodium amide, respectively. Amagasa and co-workers (15) have studied the system sucrose-liquid ammonia and have described a method for the determination of the vapor pressures of unsaturated solutions of sucrose in liquid ammonia. Certain empirical equations relating concentration, vapor pressure and temperature, and vapor pressure have been proposed for this particular system. It has been observed that glycogen dissolved in liquid ammonia does not diffuse through a cellulose membrane permeable to sucrose (16). Measurements of the overvoltage of hydrogen on certain metals in liquid ammonia have been made by Pleskov (17). The overvoltage of hydrogen on nickel
was measured a t 50.0°C. with current densities ranging from 10-'to A m p . / ~ m .in ~ a 0.1 Nsolution of ammonium chloride in liquid ammonia. The absolute values of the overvoltage were found to be higher by 0.2 V. than those in aqueous solutions of hydrogen chloride. In the case of the mercury electrode, a difference of 0.8-0.9 V. was observed, but accurate measurements could not be made because of the formation of ammonium amalgam during electrolysis. Preliminary studies using a lead electrode showed that the overvoltage is greater in ammonia than in water, but experimental difficulties prevented the determination of accurate values. The increase in hydrogen overvoltage in liquid ammonia is attributed to the greater affinityof the ammonia molecule for the proton. The electrolytic reduction of nitrobenzene, nitrosobenzene, phenylhydroxylamine, azoxybenzene, and azobenzene in the presence of ammonium chloride and sodium chloride in liquid ammonia h p been studied by Shiba and co-workers (18). The reactions were carried out in a modified Baly tube with an aluminum anode, nickel cathode, and an asbestos diaphragm. The reduction products of azoxybenzene and azobenzene were identified by comparing their absorption spectra in liquid ammonia. The results of this investigation are summarized. Na n-benzenedizotate Nitrobenzene
WrN(Na)ONa
NHIC~
Unchanged Unchanged
NHCI
NaC1 NaCl PhenylhydroxylarnineNitrosobenzene
?
fluence of 2 N solutions of neutral salts such as sodium bromide, nitrate, iodide, and perchlorate upon the catalytic action of 0.1 N ammonium chloride and bromide. It was found that an increase in the acid concentration and the addition of neutral salts changed the specific activity of ammonium salts in the same manner, the catalytic activity increasing in the following order. Further studies have also been made (20) on the influence of ammonium salts upon the rate of ammonolysis of santonin in liquid ammonia a t 20°C. The rate constant was measured using solutions of ammonium TABLE 2 Temperature ('C.) Solubility (g. NaNHr/lOOO g. NHd
20 0.16
10 0.14
0 0.14
-10 0.13
-a0 0.11
salts of weak mineral acids, carboxylic acids, phenols, amides and imides of carboxylic acids, derivatives of aqno- and ammono-carbonic acids, nitroaniline, nitromethane, and carbazole. An extensive study of the acid-base properties of various indicators in neutral, acid, and basic solutions in a number of non-aqueous solvents including liquid ammonia has been made by Shatenshtein (21). In the preparation of urea, in forty per cent. yield, from liquid ammonia and gaseous carbon dioxide, the heat of formation of urea has been found to be 7000 cal./gram molecule of carbon dioxide (22). In an earlier review (23) reference has been made to the publication of Freed and Thode (24) concerning the non-existence of colloidal solutiorrs of sodium in .. liquid ammonia. XI.
INORGANIC REACTIONS
The triammonates of gallium and indilirp trifluorides have been prepared by extracting the corresponding NaCl f I. trihydrates several times with liquid ammonia, folThe rate of amrnonolysis of pilocarpine in liquid am- lowed by treatment with gaseous ammonia a t room monia has been studied a t 0°, lo0, 20'. and 30" in the temperature (25). This procedure was necessitated presence of ammonium salts including HCOaNH4, by the fact that fluorides, in general, show less tendency C&COsNHa, CHaCOsNHb NHaC1, NHaBr, NHaNOs, to combine directly with ammonia than do other halNHJ, and NHlClOl a t concentrations ranging from ides. Although some evidence of the formation of 0.1 N to 5 N by Shatenshtein and Markova (19). GaFr2NHs and InFs2NHa was obtained, the existence The ammonolytic reaction is believed to proceed as of these diammonates was not definitely established. The preparation of a yellow octammonate of europium follows. dichloride, EuCls8NHs, has been reported (26). Decomposition of this substance results in a pale yellow CHrCH-CH-CH-C-NCHI compound which is believed to be the monammonate. I 1 11 I f NHs + 0:C CHZ HC CH The results of studies of the vapor tension and heat of formation of ammonates of the alkaline earth per'0' \N/ chlorates, Ca(C10&,6NHa, Sr(ClO&7NHs, Ba(ClO&6NHa, and magnesium perchlorate, Mg(C10&6NHs, have been reported (27). It was found that the heat of formation and stability increase with decrease in size of the cation. Foster and co-workers (28) have shown that a numThis study also included the determination of the in-
I
ber of ammino compounds are formed between triphenyl lead chloride and liquid ammonia a t its boiling point. None of these compounds is stable a t room temperature. The composition of the compound of highest ammonia content is believed (tentatively) to be expressed as the ratio of 1 mole of the chloride to 9.72 moles of ammonia. In no case can the composition of these compounds be expressed as the ratio of small whole numbers. Treatment of symmetrical dimethyldiborane with liquid ammonia a t low temperatures has been shown to result in the formation of the diammonate, (CHa)zBzHc2NHs (29). The influence of factors such as time, temperature, ammonia concentration, water content, and autoclave charge density, on the quantity and availability of nitrogen fixed during the ammonation of Capac (Michipan). peat - by liquid ammonia has been determined (30). Of these factors; only time and temperature of amm&tion exert appreciable effects. Maximum hation of nitrogen was obtained by heating the peat with liauid ammonia in an autocalve for three to five hours a t temperaturesfrom 130' to 180°C.
-
NH.H2S0,
+ 2NHa
(NH&SO, 3[NHl- NS NHs -+
+
+ [NH]
ZH:N-H:N;N:H
The action of liquid ammonia a t -33' on certain sulfur trioxide addition compounds [CsH5N.S08,C6HsN(C&)z'S08, O(CHZCHZ)ZO-SO~, HCl.SOa, and NaC1.SOs] has been shown to result in the formation of ammonium sulfamate, NHISO~NH~, together with relatively smaller quantities of triammoninm imidodisulfonate, NHaN(SOsNH&, and ammonium sulfate (33a). These reactions are believed to be ammonolytic in character. Certain relationships between "solvolytic" reactions in water, amines, and liquid ammonia, and the occurrence of acid-catalyzed reactions in these solvents have been discussed (34). 3. Reactions of Solutions of Metals The compound; commonly known as the alkali tetroxides, %Oh, represent the end-products of the action of oxygen on liquid ammonia sofutions of the alkali metals. Helms and Klemrn (35) have prepared the potassium, rubidium, and cesium compounds by passing oxygen gas into liquid ammonia solutions of these metals a t -30' to -50' for one-half day. Study of the paramagnetism, crystal structure, and stereochemistry of these substances has led to the conclusion that they are not "tetroxides" but rather "monoalkali dioxides," MOz. Attempts by Pierron (36) to prepare pure oxides of lithium by passing oxygen gas into a liquid ammonia solution of lithium until the blue color was discharged led to the formatim of mixtures of LizO and Li20z. Pierron indicates that extensive studies of modifications of experimental conditions made in an effort to secure pure Liz02 were unsuccessful. Experimental procedures used by IUemm and coworkers (37) in the preparation of the pure monosulfides, monoselenides, and monotellurides of sodium, potassium, rubidium, and cesium have been described in considerable detail. These substances were prepared in the usual manner; i. e., by interaction of the elements in liquid ammonia. The reduction of bismuth oxyiodide in liquid ammonia a t room temperature by means of sodium and potassium has been found to occur in accordance with the equation (38)
Yellow, amorphous, silicon monochloride (prepared by the thermal decomposition of Si~aCleaHz)has been shown to undergo arnmouolysis when treated with liquid ammonia a t room temperature or a t temperatures below O°C. (31). Ammonolysis is accompanied by liberation of hydrogen and results in complete removal of chlorine. The available evidence indicates that the monochloride, (SiCI),, is a highly polymerized substance involving very long chains of silicon atoms. Upon reaction with ammonia, rupture of the chain results in products containing chiefly six and eight atom chains and having the formulas, Sie(NHa)s(NH)z and Sis(NH&(NH)1 By analogy with carbon chemistry, the structures of these substances may be represented as involving alternating double bonds, with an imino group a t each end of the silicon chain. + The ammonolysis of zirconium tetrabromide by liquid ammonia a t or above 0°C. has been shown to result in the formation of the ammonobasic salt, Zr(NH)s,7NHgBr5NHa (32). This salt is soluble in liquid ammonia in the presence of an excess of ammonium bromide. The action of potassium or potassium amide on the ammonobasic salt yielded a mixture The latter salt was BiOI + 3M NHI Bi of Zr(NHh and Zr(NKh.2NH8. MI MOH MNH. . .~ Zr- The use of excess alkali metal resulted in the formation found to 'be ammonol~zed (NH)~]a t 0' and to be converted to Z ~ ( N H ) S . ~ N Hof ~ -bismutbides. The reaction between bismuth oxyBr5NHa in the presence of excess ammonium bromide. iodide and potassium amide in liquid ammonia at room The interaction of aminomonopersulfuric acid and temneratnre - - -r ~ -~ ~ ,,ie1ded >.--~ ~ ~bismuth ~ - ~~ ouvami~e. ..., liquid ammonia has been shown to result in the preBiOI f KNH* BiONH3 f KI cipitation of ammonium sulfate and the formation of a s'lution possessing both oxidizing and reducing prop- Under similar experimental conditions, silver oxide and erties (33). The violent decomposition accompanying bismuth trioxide are reduced to the corresponding metthe evaporation of the liquid ammonia is attributed to als by the action of liquid ammonia solutions of pothe decomposition of free NH groups or of the unknown tassium (39). Cupric oxide is reduced to cuprons oxide diazeue, diimide, the formation of which is shown in the while the latter is reduced to elemental copper to a last of the following equations: limited extent. Germanic oxide, GeOz, is not acted
-
+
~~~
+
-
+
upon either by potassium or by potassium amide in liquid ammonia. The reaction between phosphine and calcium in liquid ammonia a t -70' has been shown (40) to pmceed as indicated by the equation, 2PHs
-
+ Ca + XNHI
+ + (r - n)NH*
ca(PHn)rmNH~ HI
The ammonate, Ca(PHa)r6NHa, decomposes a t O°C. with formation of a diammonate. Both of these substances are spontaneously idammable in air. Foster and co-workers (41) have shown that hexaphenyldilead, (CeH&Pb-Pb(CsHs)s, may be prepared readily by the reduction of triphenyl lead iodide with sodium, or by the reduction of triphenyl lead chloride with tetrasodium nonaplumbide, NaPbs, in liquid ammonia a t -33'C. No evidence of reaction resulted from the addition of ammonium bromide to a liquid ammonia solution of sodium triphenylplumbide, (Cr H&PbNa. The disodium salt of sulfamic acid, NaNHS020Na, has been formed by the reaction of sulfamic acid with excess sodium in liquid ammonia (42). The sulfamates, M(OS02NH2)B.xHe0, of La, Nd, Sm, and Y, have been found to be insoluble in liquid ammonia (43). 111.
ORGANIC REACTIONS
The ammonolysis of the methyl ester of a-hydroxy-
(2,4,6-trimethylbenzoyl)valeric acid has been found to
and liquid ammonia a t 0' and atmospheric pressure have recently been measured (52). It was found that the rates of reaction are primarily dependent upon the electrochemical character of the radical, with stearic hindrance being a factor of secondary importance. The ammonolysis of 2,4,6-tribromopyridine by liquid ammonia in a sealed tube a t 130°C. over a period of twenty-four hours has been shown to result in the formation of 2,6-diamino-4bromopyridine together with a small quantity of an amino-dibromopyridine (53). Small and Palmer (54) have reported that the action of liquid ammonia on a-chlorocodide results in the loss of the halogen atom in the 6-position and the substitution of an amino group in the &position. The reaction was carried out in a sealed tube over a period of twenty-four hours a t 50°C. Under similar conditions, the corresponding bromo compound was relatively umeactive and most of the starting material was recovered unchanged. The addition of ether solutions of hexynyl magnesium halides (55) to liquid ammonia has been shown to result in the formation of amorphous white precipitates. The composition of these materials is illustrated by the formula CJ&C=CMg.NHr.2MgXrMg(NHz)26NH3. Allen and Henze (56) have found that 4-chloro-4-ethoxymethyIheptaneis unreactive toward both liquid ammonia a t -33.5' and solu.tions of sodium amide in ammonia a t the same temperature. Bisbromopentaerythritol does not react with liquid ammonia a t room temperature (57). At 100°C., however, there occurs a reaction leading to a mixture from which no definite product has been obtained. Dioxaspiroheptaneis not attacked by liquid ammonia a t 100°, but is decomposed completelyat 900".
result in the formation of the corresponding amide, (CH3)3CeH2CO(CH2)aCH(OH)CONH2, in nearly quantitative yield (44). The reaction was carried out by allowing the ester to react with liquid ammonia in a 2. Reactions of Solutions of Metals sealed tube over a period of four days a t room temperature. The arnmonolysis of fatty oils has been investiThe reduction of diethyltin, triethyltin, tetraethyltin, gated by Audrieth and co-workers (45). Olive, cotton- diethyltin bromide, triethyltin bromide, and triethyltin seed, maize, soybean, castor, linseed, perilla, and tung hydroxide by means of liquid ammonia solutions of sooils and pork lard were ammonolyzed to mixtures of the dium has been investigated (58). In the cburse of this corresponding fatty acid amides by liquid ammonia a t study, the following reactions were carried out: 25", both in the presence and absence of ammonium (C2H38n 2Na (C2Hd8nNa~ chloride (an acid catalyst). To a considerable degree, this work duplicates the earlier investigations of Z(C2Ha)lSn f 2 Na (CnHs)nSn(Na)Sn(Na)(GH.)r Shatenshtein and Israilevic (46). (CnHdrSn f Na (C2H3BnNa The production of acid amides by the action of liquid (C2H.)rSnNa C.HrBr (CnHdrSn + ~ a ~ r ammonia on lactones has been reported for the following ( C S H ~ J 2Na ~~ (CH&SnNa CIHrNa cases: d-a,a-mannooctonic lactone (47), 2,3,4-trimethyl d-mannonolactone (47a), 4,6-dimethyl-d-galactonolac(GHMnBrr + 2Na (C2Hs)d3n + 2NaBr tone (48), 2,4,6-trimethyl-d-iodono-&lactone(49). The (C;H$aSnBr Na (C~Hddnf NaBr polymer prepared by the action of a boron fluorideNa (C,HdsSn NaOH (C2Ha)sSnOH ether complex on a-angelica lactone has been found to react with a mixture of dioxane and liquid ammonia a t By similar reactions, Gilman and Bailie (59) have prepared a number of organolead compounds. The reac150-160" to form a polylactam (50). Marvel and Duulap (51) have shown that the action tions employed are illustrated by the following equaof liquid ammonia on vinyl chloride polysulfone causes tions, in which R represents an aryl or substituted aryl the complete removal of the chlorine and the partial re- group : moval of sulfur dioxide. R8Pb NaX QPbX + Na The rates of reaction between dimethylketone, methRaPbNa NaX RsPbX + 2Na ylpropylketone, methylphenylketone, l-methyl-cycloR,Pb f NaX RIPbNa + RX hexan-3-one, 1-methyl-cyclohexan-4-one, benzaldehyde,
+
+
+
+ +
-----
--
+
+
+
+
Attempts to prepare substituted lead hydrides of the type, RsPbH, by means of the reaction
has been prepared by adding a benzene-ether solution of the 3-en01ethyl ether of androstenedione n
were unsuccessful. The products obtained were trivalent organolead compounds, lead bromide, and RH compounds. The action of sodium in liquid ammonia on esters such as ethyl isohutyrate, ethyl benzoate, and ethyl trimethylacetate has been studied by Kharasch and co-worken (60). They have suggested the following scheme as an explanation of the mechanism of the reduction of estersby sodium. RCOnEt
ONa
ZR-C
' I\om
-
-
-
RC:O
1
RC:O
+2EtONa
RCONa
I
RCONa
+ ZEtONa
A study of the reduction of 2,3-diphenylbutadiene (61) has shown that this substance, when dissolved in a mixture of ether and liquid ammonia a t its boiling point and treated with a liquid ammonia solution of sodium, reacts to form mes0-2~3-diphen~lbutane in fifty-five per cent. yield, together with an aromatic oil and a small amount of a solid product believed to be a bimolecnlar reduction product. The preparation of dimethylacetylene in eighty per cent. $eld from sodium acetylide, sodium amide, and methyl sulfate in liquid ammonia a t -80°C. bas been reported (62). Attempts to prepare th& substance from sodium methylacetylide and methyl sulfate gave unsatisfactory yields. In the course of studies on metalation, Gilman and Bebb (63) have shown that ethynylsodium and ethynylpotassium fail to metalate 1-heptyne to any appreciable extent. Ethynyl sodium was found to metalate phenylacetylene, while slight metalation occurred with heptynylsodium and P ~ ~ Y acetylene. These experiments indicate the following order of decreasing acidity:
>
CsHIIC=CH
Pregnenin-17-01-3-one OH
0
> HC=CH
. - < .
0
-
Na
CsHIkCH
to a solution of potassium acetylide in liquid ammonia followed by de-etherification (64). An attempt to introduce a carbomethoxy group into 3-phenylcyclopentanone by the action of ethyl chloro- - acetate on tde product obtained from 3-ph&ylcyclopentanone and sodium in liquid ammonia was unsuccessful (65). The reaction product proved to be a mixture of unchaneed ketone and ~henvlcvclo~entvli. dene- (pheny1)-cyclopentanone,
A ninety-three per cent. yield of 1,3-dimercapto-2,2pentamethylenepropane has been obtained from the reaction between a solutionof sodium in liquid ammonia and an ether solution of 2,3-dithia-5-spirodecane (66). /CH-CHz\ /CHz-S /CH-CH2\ /CHzSH H9C I -H*C \CH~CH~/~CH-S \CH-CH/C\CH,SH .
.
Similarly, bishydroxymethyl.bis~ercaptomethylmeth. ane was prepared in 87.5 per cent. yield from 4,4-bishydroxymethyl-l,2-dithiacyclopentane.
-
/CH-S (CHsOH)zC\ 1 C H
/CHaSH (CH20H)zC ~ \CH~SH
Treatment of an ether solution of 4,4-dimethyl-1-thio1,2-dithiacyclopentane with sodium in liquid ammonia has been found to result in a ninety-four per cent. yield of 1,3-dimercapto-22-dimethylpropane. /CH-S:S (CHa)sC \CH>-S
-
I
(CHW,
/CH,SH CHSH
I -The synthesis of d- and gN, Nt-dimethylcystine has been accomplished by du Vigneaud and co.workers (67) by means of the following reactions.
+
-
[HOXCHN(CH~)(SOZCGHI)CHI]&Na H02CCH(NNCHJCH&3Na H02CCH(NHCHS)CH&Na CaH.CH2CI HOsCCH(NHCH1)CHdCH2C6H6 HOsCCH(NHCHs)CHdCH1CeH6 Na H02CCH(NHCHs)CHd I2 [HOaCCH(NHCH,)CH~I&
+
- -
+ +
Thus, N,Nf-dimethyl-N,Nf-his-(9-tolylsulfonyl) cystine was reduced by sodium in liquid ammonia and the reduction product allowed to react with benzyl chloride. The resulting S-benzyl-N-methyl cysteine was then
treated with sodium in liquid ammonia and the Nmethylcysteine so formed was oxidized to the disnlfide by the addition of a solution of iodine in ether. dlCystine has been prepared in eighty per cent. yield by the reduction of S-benzyl-dl-cysteine with sodium in liquid ammonia, followed by oxidation of the resulting sodium cysteinate (68),
HOICCH(NH1)CH2SNa
lo I + HOH
ucts obtained with sodium and those resulting from reactions involving calcium. In the 6rst column of Table 3 there are listed the hydrocarbons reduced and in the second column the products identified. TABLE 3
.
"vdrornrhon ---~~-~~~
Naphthalene (-75O to -65') Naphthalene > 65') ~ a p h t h a ~ c n1 e- 3 3 . 5 ~ Al-Dihydranaphthalene A'-Dihydronaphthalene Biphenyl [HOICCH(NHI)CHXI~SI3.4-Dihydrobiphenyl Terphenyl
Producl(d.
AL-Dihydronaphthalene A'- and Al-Dihydronaphthal~ne a*-and A*-Dihydronaphthalene A'-Dihydron.phthalene Tetralin 3 4-Dihydrobiphenyl 3'4,5,6-~etrahydrobiphenyl 3:4L~jhydroterphenyland a mmpound.
S-Benzyl-1-cysteine has been obtained in eighty-five per cent. yield by the reduction of 1-cystine with sodium in liquid ammonia followed by the addition of benzyl chloride to the reduction product (69),
It is also reported that upon reaction with a solution of sodium amide in liquid ammonia a t -70°, A2-dihydronaphthalene is converted quantitatively to A1-dihydronaphthalene. In connection with their studies on the origin of formBy reduction of S-benzyld-cysteine with sodium in aldehyde obtainable from lignin, Freudeuberg and liquid ammonia followed by oxidation of the reduction product there was obtained an eighty-six per cent. yield co-workers (74) have found that formaldehyde cannot be obtained from lignin which has been pretreated with of d-cystiue. a liquid ammonia solution of potassium in a sealed tube over a period of fifteen hours a t 20°C. That the . . [OI methylenedioxy groups in lignin are aromatic in characNaO3CCH(NHz)CHdNa--t [HO82CH(NHa)CHll& - ter is indicated by the fact that certain aromatic methHOH ylenedioxy compounds behave similarly toward potasS-Benzyl-Lcysteiuehas been prepared by reduction of sium in ammonia under comparable experimental cystine with sodium in liquid ammonia followed by conditions. Thus, when dihydrosafrole was treated with a solution of potassium (and potassium amide) for addition of benzyl chloride (70). The reduction of both p-geraniol and p-liualool has twenty-four hours a t room temperature, it was conbeen shown to result in the formation of pmethyl- verted to p-hydroxyphenylpropane:, Piperonylic acid geraniolene (71). The reactions were initiated a t similarly treated for fifteen hours a t 15-20' yielded mtemperatures considerably below the boiling point of hydroxybenzoic acid. This and other evidence leads the solvent by adding an absolute alcohol solution of to the conclusion that the formaldehyde obtainable is present largely in aromatic methylene8-geraniol or p-linalool to a solution of sodium in liquid from lignin ammonia. After volatilization of the ,ammonia, the dioxy groups. The - - - - use - ~ - of ~- liauid ammonia as a medium for the forreduction products were treated with water. An unsuccessful attempt has been made to separat8 geraniol mation of cellulose xanthates has been investigated (75). and citronellol through the reduction of the geraniol by Trisodium cellulose was prepared by the interaction of sodium and cellulose in liquid ammonia and thereafter means of sodium in ammonia (72). The reduction of a number of unsaturated and poly- treated with carbon bisulfide in the same solvent. The nuclear aromatic hydrocarbons by means of solutions formation of the sodium salt was accelerated by the of sodium and calcium in liquid ammonia has been presence of sodium halides, and the 'eaction with carstudied by Hiickel and Bretschneider (73). Most of bon bisulfide was accelerated by the presence of sodium these reactions were carried out a t temperatures within nitrate. The xanthates produced in this manner were the range -75" to -60°C., although in a few cases soluble in water. The reaction between 2,3,4-trimetbyllevoglucosau higher temperatures (up to -33.5') were employed. The use of ether as a diluent was found advantageous and sodium in liquid ammonia has been shown to resince it facilitated the solution of the hydrocarbon mate- sult in the formation of phenol (75a). Thus, 0.55 rials and permitted more accurate temperature control. gram of phenol was obtained from 3.86 grams of the As has been observed in earlier studies of reactions of carbohydrate in a reaction carried out in a sealed tube this type, the primary reduction products frequently a t room temperature over a period of 18 days. The behavior of insulin toward sodium in liquid amconsist of alkali or alkaline earth metal salts which form colored solutions in ammonia. Upon completion monia has been shown to be similar to that of casein, of the primary reduction process, these salts were egg albumin, edestin, and silk fibroin (76). With retreated (in liquid ammonia) with ammonium chloride. spect to its action in lowering blood sugar, insulin was Only in the case of 1,4-diphenylbutadiene did there found to be inactivated completely by treatment with appear to be any marked difference between the prod- small amounts of sodium. Crystalline insulin after ~
~
280
JOURNAL OF
being dried a t 80°C. was found to be soluble in liquid ammonia without appreciable change. M i e r and Roberts (77) have studied the behavior of a number of peptones and related substances toward sodium in liquid ammonia. It was found that peptones in liquid ammonia are more acidic than diketopiperazine, but less acidic than proteins or amino acids. This study indicates that peptones contain relatively more diketopiperazine than do proteins.
CHEMICAL. EDUCATION
so formed is subsequently treated with a monohaloamine. In another patented process, products such as cellulose acetobutyrate (84), cellulose acetate stearate (85), cellulose acetate propionate (8'3, or other saturated fatty acid esters of cellulose (87) are stabilized by treatment with and subsequent separation from anhydrous liquid ammonia. This method has also been applied in the stabilization of cellulose acetate and carbohydrate derivatives such as starch stearate (88). The 3. Other Organic Reactions separation of cellulose diacetate from insoluble cellulose Kharasch and Sternfeld have shown that sodium triacetate (89) has been accomplished in a process which amide in liquid ammonia may be used successfully as a depends upon the solubility of the former in liquid amcondensing agent in the preparation of hexatriene and monia in the presence of an acid catalyst. The product obtained by the interaction of phosphorus pentoxits polymers from ally1 chloride (78). ide and liquid ammonia has been used to impregnate NaNHn H~C:CHCBC~ + C]CH&H:CH~-H~C:CHCH:CHCH:CH~ cellulosic materials such as textile fibers, paper, or regenerated cellulose for the purpose of producing flameThe formation of bexatriene was accompanied by the proof products production of high boiling products in quantities deA, has been befor a number of years, a considerpendent upon the particular experimental conditions able number of patents issued on processes involving in One instance there was obtained the use of liquid ammonia center about the problem of a fifty per cent. yield of l-chlorometh~l-2-vin~lc~clopreparing organic ,,itrogen such as amides, hexene-3. The polymerization of hexatriene is believed a ~ n e s ,nitriles, and so forth, Thus, formamide is to be promoted by high concentrations of s o d i m formed from carbon monoxide and liquid ammonia in amide. the presence of a suitable catalyst a t temperatures beIt has been observed that no reaction occurs between tween O,O and and pressures ranging between thiourea and 2-chlorobenzothiazole in liquid ammonia and atmospheres (91), Acid amides and glycerol a t -33.5' or a t room temperature either in the presproduced by treatingfats with liquid ammonia in ence Or absence ammonium bromide (79). Both the presence of ammonium salts, inorganic acids, or compounds, however, enter into reaction with the sol- metal amides at 20-400 and under pressures of 8 to 15 vent under the above conditions. atmospheres (92). Amino nitriles a r e prepared from have wed liquid ammonia hydroxy nitriles such as formaldehyde cyanohydrin by Robe* and Horvitz with liquid ammonia under in the preparation of conjugation products of epineph- treatment at 75fine with glycine, t~rosine,glutadc acid, urea. lactic 8ooc. (93). A method for the production of melamine acid, dextrose, cholesterol, and vitamin C. The physio- (2,4,6-triamino.1,3,5-triaZine) involves the action of logical activity (increase in blood pressure) of all of the liquid ammonia under at elevated temperaproducts that with was greater tures on cyanamide, ammonium thiocyanate, methylthan that of epinephrine. sulfocyanurate, cyanuric chloride (94), or dicyanodi* amide (94, 95). In another process, trichloroacetamiIV. PATENTS dine (96) is formed by treating trichloroacetonitrile A number of patents issued during the year relate with an excess of liquid ammonia a t -40°C. Other to the preparation of derivatives of cellulose and to the related compounds and their derivatives may be pretreatment of various cellulosic materials. Peterson pared similarly. Ammonium imidosulfonate and amand Barry have patented methods for the preparation of monium amidosulfonate (97) are fbrmed by introducing cellulose ethers. One process involves the formation liquid ammonia and sulfur trioxide into a suitable reacof sodium cellulose by the treatment of cellulose with tion chamber maintained a t an elevated temperature. sodium (81) in liquid ammonia a t its boiling point in The use of an excess of ammonia is specified. Reaction the presence of an inert hydrocarbon diluent such as in liquid ammonia is involved in a process requiring the toluene, followed by the addition of, for example, ethyl formation of sulfonamides which are subsequently conbromide. A similar process ditTers to the extent that verted to the corresponding chloromethyl compounds the alkali cellulose is formed by the interaction of cellu- (98). Thus, octadecylsulfouamide is formed by the lose and an alkali amide (82), such as sodium amide, in reaction between liquid ammonia and octadecylsulfonyl liquid ammonia followed by volatilization of ammonia chloride. and by etherificatiou in a solvent such as toluene. The A patent issued to Miller and Roberts (99) and asextent of salt formation is governed by the quantity of signed to the du Pont Company is of interest. This alkali amide used. The use of alkali cellulose formed patent, concerned with a process for the "production of from cellulose and an alkali metal in liquid ammonia finely divided sodamide," was applied for under date of has also been suggested in a method for the preparation September 13, 1934, and issued as of June 20, 1939. of aminocellulose derivatives (83). The alkali cellulose A method accomplishing essentially the same result was
,
'
described in a paper submitted by Nieuwland and coworkers (100) under date of July 2, 1934, and published in October of the same year. The process involves the formation of sodium amide by the reaction between sodium and liquid ammonia at its boiling point in the presence of a catalyst consisting of a compound of iron. The authors quote from the patent, "Table 2 lists the compounds of iron which we have found to catalyze the reaction between sodium and anhydrous liquid ammonia. They show their catalytic effect without the presence of metallic iron." One of the compounds listed is ferric nitrate. The earlier work of Loam (101) as well as that of Nieuwland and coworkers (100) has shown that ferric nitrate is reduced to finely divided and highly reactive metallic iron under the experimental conditions disclosed in the patent. This, together with other evidence (102) would tend to indicate that in cases involving the use of an iron compound as a catalyst for the reaction in question, satisfactory catalytic action results from the presence of metallic iron formed by the reduction of the iron compound employed. The removal of water and impurities such as chlorides and chlorates from aqueous alkali metal hydroxides (e. g., NaOH) has been accomplished by a process involving extraction of the material to be purified with liquid ammonia (103). Either anhydrous ammonia or mixtures of liquid ammonia and limited quantities of water may be used. Patents have been issued on methods for producing improved nitrate explosives consisting of a finely divided sensitizer such as aluminum, sulfur, or dinitrotoluene (104) or nitrostarch (105) uniformly dispersed in solid ammonium nitrate. The dispersion is effected by suspending the sensitizer in a liquid ammonia solution of ammonium nitrate and thereafter evaporating the solvent ammonia. Another patent relates to the use of liquid ammonia in the production of mixtures of ammonia, hydrogen, and nitrogen which are suitable for use as fuels for internal combustion engines (106). I.
V.
GENERAL
In designing an apparatus for the dispensing of dry gaseous or liquid ammonia, advantage has been taken of the marked deliquescence of ammonium thiocyanate in the presence of gaseous ammonia (107). The gas from the commercial cylinder is absorbed in dry ammonium thiocyanate and thereafter liberated, as needed, by the application of heat. The necessary apparatus is described in detail. The second in a series of monographs by Shatenshtein (108)has appeared within the year. Thisvolume is concerned with experimental procedures which are available for the utilization of liquefied gases as solvents and reaction media, and includes a bibliography on the solubility of inorganic substances in liquid ammonia. Those portions of the book which deal with electrochemical methods were written by V. A. Pleskov. Wildt (109) has suggested that the atmosphere of the planet Jupiter consists largely of ammonia and that certain colored bands may be due to the formation of solutions of sodium in ammonia while other bands are attributed to the presence of sodium amide, which results from the reaction between sodium and ammonia. Certain interesting relationships between the solubility of intermetallic compounds in molten salts and in liquid ammonia have been pointed out by Heymann and Weber (110). Properties of liquid ammonia solutions in their relationship to basic problems in electrochemistry have been discussed by Frumpkin and Pleskov (111). :, ACKNOWLEDGMENT
The authors wish to acknowledge their indebtedness and express their thanks to Dr. Otto Reinmuth. As Dr. Reinmnth has, over a peeditor of Tms JOURNAL, riod of seven years, offered many helpful suggestions and granted many favors for which we are truly grateful.
LITERATURE CITED
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