mm
A MM0N 0LYSIS
GERALD H. COLEMAN
DOW CHEMICAL COMPANY, MIDLAND, MICH.
,-
L
There has been considerable interest in the past year with regard to the broad field of ammonolysis. Most of the references have involved the reactions of ammonia or amines with haloorgantcs, aldehydes and ketones, the preparation of amides and resins, and cyclizations. Amines have been prepared catalytically in high conversion and yield from alcohols, ammonia, and hydrogen. Work has been continued on forming alkanolamines from olefin oxides. Nitriles were made in various ways. Azomethines have been prepared frequently. The Mannich reaction gives interesting products. Work on reductive amination is continuing. O n e of the most prolific fields is that of cyclization to prepare pyridines, piperidines, quinolines, pyrroles, morpholines, and others. Investigations of quaternary ammonium compounds are proceeding, and ion exchange resins are of increasing importance.
A
S IN the past, the designation ammonolysis is interpreted to cover amines as well as ammonia. The intent has been
to deal with the present subject quite broadly with emphasis placed on industrial interest.
REACTION OF ESTERS WITH AMMONIA AND AMINES Fatty acid amides are prepared commercially from fatty acids rather than fats. Roe et al. (90) studied the direct conversion of fats t o amides and glycerol by reaction under pressure with liquid ammonia or amines, obtaining practically quantitative yields of amides from oleo, olive, castor, and tobacco seed oils. Anhydrous liquid ammonia led to higher yields than did aqueous ammonia in the ammonolysis of methyl oleate (Table I).
Table 1. Ammonia
Heating an aromatic or heterocyclic amine with phenyl benzoate in 1-methylnaphthalene o r 1 , 2 , 3 , 4 tetrahydronaphthalene a t 180" to 200" C. for 2 to 3 hours produced the N-benzoyl derivative of the amine in 26 to 91% yield by Takatori and Ueda (108). In the absence of solvent, the mixture is heated 2 to 3 hours a t 180" to 200" C. for heterocyclic amines and 3 to 5 hours a t 200" to 230" C. for aromatic amines. 2-Benzoylamino-6-methylbenzothiazole was obtained in 91% yield. The reaction of methyl esters of a number of carboxylic acids (not readily decarboxylated) with excess benzyldiethylamine was studied a t about 200" C. in a nitrogen atmosphere in the absence of solvents by Eliel and Anderson ( $ 2 ) . Products were trimethylamine and the benzyl ester of the acid. Yields were usually 70 to 97% based on ester employed and on 50 to 97p/, conversions. The equation follows: RCOOCH3
Ammonolysis of Methyl Oleate Temp., Time, Yield c. Hours Oleamide, % '
Oleo was reacted with liquid ammonia a t 170" t o 175' C. (98% yield), with n-dodecylamine a t 230" C. (9895 yield), and with ethanolamine under reflux (95% yield). Phillips (80), continuing his previous work, prepared a series of bis-p-piperidinoethyl and p-pyrrolidinoethyl amides of aliphatic dicarboxylic acids (oxalic to sebacic) by refluxing-e.g., 1 mole of methyl or ethyl dicarboxylates with 2.5 moles of piperidinoethylamine a t 190' C. for 4 to 24 hours. Yields were 60 to 90%. N,N-Diethylacetoacetamide, of interest as a possible insecticide, was made in 65% yield by Utzinger (104) by a temperature modification of previous methods, passing diethylamine vapor into boiling ethyl acetoacetate. Gruber et al. (39) improved the known process of preparing esters of aminocrotonic acid from acetoacetic acid esters and ammonia by carrying out the reaction in the presence of alcohols such as cetyl alcohol. This is to prevent discolored products which are stabilizers for chlorine-containing synthetic resins. Introducing ammonia during 10 hours into a mixture of cetyl acetoacetate and cetyl alcohol gave a colorless product consisting of cetyl aminocrotonate and cetyl alcohol. Tetramethylene glycol functioned similarly.
+ CeHbCH,N(CH,),
+
RCOOCHzCsHs
+ N(CH3)3
The reaction rate seemed to increase with increasing strength of acid with a corresponding decrease of reaction time and temperature. The only by-product usually obtained was a small amount of the free acid.
REACTION
OF AMMONIA AND AMINES WITH ALCOHOLS
Kozlov and Akhmetshima (68) found that in aminating cyclohexanol with ammonia with alumina catalyst in a flow system to form cyclohexylamine and water, formation of by-product cyclohexene by dehydration can be practically suppressed by carrying out the process under increased pressure (8 to 10 atmospheres of ammonia). The dehydration side reaction is intense under 1 atmosphere but amination becomes predominant under 5 t o 10 atmospheresat the optimum temperature of 260 'to 300 O C. and under 8 to 10 atmospheres, the yield of cyclohexylamine is 70 to 74% of cyclohexanol passed and 90 to 95% of the amount reacted. Davies et al. ( d 6 ) produced amines by passingalower aliphatic alcohol together with ammonia and hydrogen in the vapor phase a t 240" to 300" C. and 10 to 25 atmospheric gage over a formaminate copper catalyst treated with an alkaline earth metal basic compound. Such catalysts are an improvement over the usual nickel and cobalt catalysts in giving higher conversions and yields and also a t the temperatures used the higher alcohols vaporize more readily. I-Butanol, hydrogen, and ammonia led to a 96% conversion per pass and a 97% yield based on butanol. The liquid product had the following per cent composition by volume: Butylamine Dibutylamine Tributylamine 1-Butanol Water
17 52 12 3.5 15.5
Wright and Cramer ( 1 1 7 ) reacted glycerol with a sulfonating agent to form intermediate products which then were aminated
1915
1916
INDUSTRIAL AND ENGINEERING CHEMISTRY
by treatment with 5 to 50 moles of ammonia per mole of sulfate ester group in the presence of fixed alkali and water at 0 t o 250 pounds per square inch and a t 40 O to 150" C. T h e crude glyceryl amines obtained were for use in alkyd resins.
REACTION OF AMMONIA AND AMINES WITH OLEFIN OXIDES
Vol. 45. No. 9
in acetic acid a t 140" to 145" C. As an example, p-toluidine gave a 547u yield of p-N-(2-cyanoethyl)toluidine and a 42% yield of p-.V-N-bis-(2-cyanoethyl)t~luidine. Cook and Moss ( 2 2 ) heated diethanolamine with acrylonitrile on a steam bath to obtain practically a 95% yield of crude p-di(2-hydroxyethyl)aminopropionitrile. Cocker, Cross, and PvlcCormick ( $ 2 ) react'ed diethyl aniinonialonate and ethyl aminoacetate with acrylonitrile to form, respectively, diethyl a-amino-a-(2-cyanoet'hy1)malonate and ethyl 2-cyanoethylaminoacetate; potassium hydroxide and sodium ethylate functioned catalytically. Kurtz and Schwart'z (60) prepared y(dimet~hylamino)crotonononitriles, by reacting a benzene solution of dimethylamine a t about 30" to 50" C. with 1-chloro-3-cyanopropene and 3-chloro-1-cyanopropene, in good yield. It was found that amines add t o the double bond of the esters of methacrylic acid easier than alcohols: see Bieber (6). Pietrusza ( 8 1 ) obtained 75 t,o 90% yield of nitriiotrispropionamide by treating methyl acrylate with excess ammonia a t about - 10" to 0' C. in a hydroxylated solvent (water, ethylene glycol) having a higher dielectric constant than methanol. The reaction is catalyzed by ammonium acetate. Bestian ( 6 )made the et,hylene glycol diester of p-ethyleniminobutyric acid in high yield from ethylene dicrotonate and ethylenimine a t 100" C. Erickson (33) prepared several -V,N-dialkyl-~-dialkyIaminopropionamides from heating diallryl amines with acrylates according to the equation:
During the past year there have been a number of publications on preparing amines fiom olefin oxides. I n the production of mono-, di-, and trialkanolamines, Ferrero, Berbe, and Flamme (56)56) have patented the improvement of reacting the lower alkylene oxide with aqueous ammonia in the presence of an addition of a calculated amount of either mono- or diethanolamine to suppress formation of the added component. Huscher, Long, and Moore ( 5 0 ) treated a lower olefin oxide with anhydrous alkmolamine in given molar ratios to obtain polyalkanolamines. For instance, 20 moles of liquid ethylene oxide were added in 3 hours to 10 moles of anhydrous monoethanolamine a t 10' C. The product contained 90.6Tu triethanolamine (by weight), 2 4% diethanolamine, and 6.7% higher boiling compounds. rvIalinovskil and Baranov ( 7 1 ) passed a mixture of ethylene oxide and ammonia, in a 3 : 1 ratio, over magnesium oxide a t 400 ' to 410" C., obtaining ethylene glycol cyclic acetal, pyrrole, and acetaldehyde-ammonia products. Picoline, collidine, and pyridine also are obtained when alumina is added. Over zinc oxide no heterocyclics are formed. Other products are obtained by R' R' catalyst variation. I A series of aryloxypropanolamines 1% hich possessed local anes2R29H CHZ=CCOOR" -+ R&CHphHCONR2 R"OH thetic activity were prepared by condensing aryloxypropylene Such aminoamides decompose on heating t o dinlkylamines and oxides Rith secondary amines by Ring and Ormerod (88). Ten N,N-dialkylacrylamides. new ether aminoalcohols were prepared by Pollard and K c k e r -4reaction analogous to the addition of ammonia or amines ( 8 3 ) from ether propylene oxides and ethylenediamine-e g . , with acrylic esters and acrylonit'rile is that of adding amines to refluxing 3-heptyloxypropylene oxide with the diamine gave acrylamide: a low yield of N,~~~'-bis(2-hydroxy-3-heptyloxypr~~p~~l)ethyleneRzNH CH,=CHCONH, + R2NCH2CR2CONH2 diamine. The compounds had amebic activity in vitro. This past year Slyern and Findley (101) heated cis-9,lOYields of 49 t o 807, were obtained by Erickson (53) by carrying epoxystearic acid at about 100" C. Tvith aqueous ammonia, out, this reaction with dimethylamine, dipropylamine, dibutylmethylamine, ethylamine, and diethylamine, and with aniline amine, and morpholine in alcoholic solution a t room temperature. -to obtain products which were either 9,lO- or 10,9-aminoHopff and Spanig ( 4 7 )treated aminophenols or aminonaphthols hydroxystearic acids. PigulevskiI and Kuranova (82) carried with a,p-unsaturated ketones in a solvent in the presence of conout the same reaction with ammonia. cent,rated sulfuric acid a t about room temperature, obtaining New S-( 3-dialkylamino-2-hydroxypropy1)phenothiazines have bactericidal products. m- [Bis(3-oxobut,yl)amino]-phenol rebeen prepared by Charpentier (19). For instance, AV-(2,3sulted from methyl vinyl ketone and m-aminophenol. epoxypropy1)phenothiazine was heated with alcoholic diethylClifford ($0)prepared 2-(2-pyridyl)ethylamines by refluxing amine a t 120" C., the product being the expected diethylamino 2-vinylpyridine with a primary or secondary amine. Starting derivative. with aniline, a 70% yield of crude X-2-( 2-pyridy1)ethylaniline
+
+
+
REACTION OF AMMONIA AND AMINES WITH UNSATURATES Ishiguro et al. (63) synthesized acetonitrole in 91% yield by passing acetylene and ammonia over a zinc oxide kaolin catalyst at 400" C. Less than 0.8% of pyridine bases were formed. Efficiency of the catalyst remained unchanged for 16 runs Other catalysts were prepared from kaolin mixed with chromium, zinc, iron, and thorium oxides, and zinc chloride and zinc sulfate. Nitriles were prepared by Teter and Olson (103) by catalytically reacting ammonia with-e.g., crude propylene a t 370" and 1500 pounds per square inch. T h e catalysts, products of mixed cobalt and magnesium oxides on diatomaceous earth, have a longer useful life, give a higher yield (357u) of nitriles, and can be reactivated by hydrogen. I n one example the product consisted of 44.5 weight 7uof propionitrile, 25 weight % ' of acetonitrile, 17.9 weight % of n-butyronitrile, 4.4 weight % ' of isobutyronitrile, 0.8 weight % of water, and 7.2 weight % of bottoms. Various amino compounds have been reacted with unsaturated nitriles to form aminonitriles. Braunholtz and hfann ( 2 2 ) heated aromatic primary amines with 2.5 moles of acrylonitiile
c.
was obt'ained.
REACTING AMMONIA AND AMINES WITH HA LOORGA NlCS Considerable u-ork was done in 1952 concerning preparing aminoorganics from haloorganics and ammonia or amines. A few references are presented below. Butler and Goette ( 1 7 ) obtained 27 to 90% yields of vinylox ox ye thy la mines by an improved process involving reacting vinyl 2-chloroethyl ether in 2 molar excess for a longer time period with secondary amines such as morpholine, diallylamine, and dibutylamine. Various propargylamines were prepared by Wolff (116) from propargyl halides and suitable amines in the presence of dry sodium carbonate. For instance, propargyl bromide was refluxed with aniline in ethyl alcohol to obtain a 31.5% yield of N-propargylaniline. Armitage and Whiting ( 1 ) made 1,6-bis(dimethylamino)-2,4hexadiyne in 50% yield b y reacting l,G-dibromo-2,4-hexadi~-ne a t 20" t o 30" C. with 25% aqueous dimethylamine. The 1,6dichloro compound reacted similarly. A3-Pyrroline has been condensed at its - N H group with aliphatic halo-compounds such as dihaloalkanes, haloaliphatic
September 1953
J
INDUSTRIAL AND ENGINEERING CHEMISTRY
acids, ethylene chlorohydrin, and chloroacetic acid by Copenhaver (23)by heating the reactants with an acid-binder in aqueous medium a t 70" to 100" C. Ethylene dichloride gave crude 1,2bis-(N-Aa-pyrroliny1)ethane. N,Nn-Dibensyl-N,N',N''-trialkyldialkylenetriamines were patented by Williams and Strobe1 (113) and were made by reacting a lower alkylamine with a lower alkylene dihalide a t 70" t o 90" C., removing unreacted amine, and alkylating with a benzyl halide a t 60" t o 70" C. As an example, reaction of anhydrous methylamine (465 grams were actually used) with ethylene dichloride (735 grams) and then with benzyl chloride (1125 grams) gave 1180 grams of product consisting of 60% symmetrical dibenzyldimethylethylenediamine, 30% of N,N~'-dibenzyl-N,N',N"-trimethyldiethylenetriamine and 10% of benzylated higher amine condensation products. Jones (64) has patented lower alkyl a-n-hexylaminooctanoates which possess high analgesic activity. They were prepared by reacting alkyl a-bromooctanoates with n-hexylamine. Craig and Exner (25)patented benzyl-tertoctylamine as a new compound. It has considerable insecticidal activity, boils a t 100" to 102' C./1.2 mm., and was obtained in 77% yield by heating benzyl chloride with tertoctylamine a t about 160" to 197" C. Sprules and Bell (96) were interested in producing benzyl type amines by an improved method. An aralkyl halide wasadmixed withcontinualstirringat 5" to 50" C. a t about atmospheric pressure with aqueous ammonia or a primary or secondary aliphatic amine, the molar ratio of the amine to the benzyl chloride being a t least 4 to 1. Yields up to 97% resulted. N Substituted aminophenols were prepared by Vaughan and Bean (105) by refluxing p-bromophenol with an alkylene polyamine, primary alkanolamine, or N-alkanol alkylene polyamine. Refluxing pbromophenol (35 grams) with aqueous ethylenediamine (40 grams) in the presence of copper sulfate catalyst gave 41 grams of the sulfuric acid salt of N-p-aminoethyl-p-aminophenol. McCracken (67) obtained new N-(thiophenealkyl)arylamines, useful as oxidation and corrosion inhibitors, by condensing arylamines with haloalkylthiophenes. Reaction of l-naphthylamine with 2-(chloromethy1)thiophene a t room temperature gave N-( 2-thiophenemethyl)-l-naphthylamine. Similar products were made.
PREPARATION OF AMIDES
f
Interest in the present industrial production of vanillin and the biological activity of derivatives caused Kratzl an! Kvasnicka (59) t o prepare a number of amides of vanillic acid and related acids by modifications of the acid chloride-amine reaction. Jones (55) patented the process of producing N-(hydroxyalky1)amides of acrylic acids by adding an acrylyl chloride to excess alkanolamine in acetonitrile as solvent. The latter is a nonsolvent for the amine hydrohalide formed in the reaction. N-pEthanol-methacrylamide resulted in 65y0 yield from ethanolamine and methacrylyl chloride. The preparation of lower dialkyl acylamides by heating a tris(dialky1amido)phosphate with excess lower alkanoic acid a t approximately the boiling point of the dialkyl acylamides is the subject of a patent to Heider (49). A 73.5% yield of dimethylacetamide was obtained by heating tris(dimethy1amido)phosphate and acetic acid under reduced pressure. Nylander (78)made nicotinic acid diethylamide in 9470 yield by treating nicotinic acid, diethylamine, and phosphorus pentoxide in the molar proportions 1:2.89 :0.94 in toluene. Nicotinamide itself was produced in yields of 75 to 99% by Wissow (116) by reacting a large excess of ammonia with nicotinic acid in a closed vessel a t 200" C. and under 1000 pounds per square inch. Mueller (76) has made acetoacetic acid amides by reacting diketene with a salt of carbonic acid with ammonia, methylamine, or ethylamine. It was found by Raczynski (86)that acrylamide can be prepared in higher yields than formerly by passing gaseous ammonia into acrylic anhydride in an inert sol-
1917
vent a t about 25' C.; there is little or no addition of ammonia to the double bond. Conversions and yields were both about 85% and up. Naylor ( 7 6 ) extended the preparation of amides by the Willgerodt reaction to aromatic carboxamides. For instance, when toluene, sulfur, and concentrated aqueous ammonia were heated in a stainless steel rocker bomb a t 270" C., benzamide was formed.
PREPARATION OF AZOMETHINES New azomethines have been obtained by Hurwitz (49) from tert-carbon primary amines and an aldehyde: RaCNHz
+ RCHO
+ R,CN=CHR
+ HzO
2ertButylamine was treated with 37% aqueous formaldehyde, tert-butylazomethine forming exothermically in 70% yield. Bisazomethines also were made. Winsten (114 ) discovered that pyridoxylidene-p-aminosalicylic acid was slowly water soluble and useful for tuberculosis chemotherapy. To make it, pyridoxal hydrochloride was mixed with sodium p-aminosalicylate in methanol. Hartough and Dickert (42) aminomethylated alkoxybenzenes t o produce N-alkylidene (alkoxyary1)alkylamine and disubstituted diarylmethanes according to the following equation : 3R'OR
+ 3CHz0 + NHiCl
---c
RtORCH2N=CH,.HCl
+ R'ORCH2ROR' + 3Hz0
-4trimer is obtained when formaldehyde is used.
Mathes (7'3) patented the method of preparing iminoesters of dithiocarbamic acids by reacting a water-soluble salt of a dithiocarbamic acid with a dithiocarbamyl aldehyde and then reacting the latter intermediate with ammonia or primary amines. A 90% yield of 2-(pheny1imino)ethyl N,N-dimethyldithiocarbamate was obtained. A procedure was evolved by Deanesly (27)for the recovery of an anhydrous azomethine from the reaction mixture without substantial hydrolysis. Unreacted amine and carbonyl compound are removed countercurrently by dry ammonia gas and the residue is then dehydrated. Bergmann and Lavie (d), on a ver*y small scale, subjected a mixture of 4,4'-diaminodiphenylmethane and ochlorobenzaldehyde to azeotropic distillation with benzene, obtaining bis( o-~hlorobenzylidene)-4,4 '-diaminodiphenylmethane in about 85% yield. 4,4'-Diaminobenzophenone was treated similarly.
MANNICH REACTION In continuing work on the Mannich reaction, Burke et al. (14-16) found that condensation of phenols with formaldehyde and primary. amines lead to N,N'-bis(hydroxybenzy1)amines directly in certain instances instead of forming benzoxazines. The nature of the substituent ortho t o the phenolic hydroxyl group plays an important role in determining the course of the reaction. In a series of six N,N-bis(2-hydroxybenzy1)aminesprepared from phenols, formaldehyde, and primary amines the yields varied from 52 t o 85'%. Related studies were made with 1-naphthol. Wiley (110, 111) prepared 3-dialkylaminomethylchromone hydrochlorides by reacting formaldehyde and a secondary amine hydrochloride with a chromone which is unsubstituted in the 2and 3-positions. Wilder and Herman (109) discovered that terthydroxymethyl ketones will react with formaldehyde and a secondary amine or its salts to produce N-disubstituted amino-1-hydroxyketones in yields up to 90%. As an example, a mixture of 2-methylbutan-2-ol-3-one1diethylamine hydrochloride, and paraformaldehyde was heated on a steam bath to obtain
4-methyl-l-diethylaminopentan-4-ol-3-one. Logan and Schaeffer (64) have extended the Mannich reaction
1918
I N D U S T R I A L A N D E N G I N E E R I N G CHEMISTRY
to use of chloroacetaldehyde and dichloroacetaldehyde. Wright and Lincoln (118) have shown that a-phenoxyacetophenones and or-phenoxypropiophenones readily undergo the Mannich reaction, yields being about 60% and higher.
REDUCTIVE AMINATION This method of producing amines is used quite frequently. Caldwell (18) prepared 2,2-dimethyl-3-hydroxypropylamineby hydrogenation of a mixture of 2,2-dimethyl-3-hydroxylpropionaldehyde and ammonia in a solvent a t 1000 to 2000 pounds per square inch a t 50" to 100" C. in the presence of Raney nickel cat,alyst. Stichnoth (97) obtained a mixture of aminomono- and diinethylcyclohexanes, intermediates for making pesticides, by passing ammonia, hydrogen, and a mixture of dimethylcyclohesanones, dimethylcycloheranols, methylcyclohexanols, and xylenols over nickel-pumice catalyst a t 170" to 180' under pressure. Suter and Zutter (100) found t h a t cat>alytichydrogenation of aryloxyacetones in the presence of ammonia did not give 2-aminopropanol ethers but the corresponding alcohols. They accordingly treated the aryloxyacetones with a n amine and effected simultaneous reduction wit,li Raney nickel catalyst a t 110 atmospheres. Stuhmer and Kauptmaiin (SD) shoived that reaction of cyclohexylamine with a#-unsaturated ketones, hydrogen, and platinum-barium sulfnte catalyst gave N-cyclohexyl-a-alkyl-~phenylpropylamine. Yields were 60 and 85%. La Forge et al. (61) obtained pharmaceutically interesting aliphatic amines in various ways. For instance, 6-oxo-heptanol and methylamine were treated with activated aluminum a t GO" t o 70" t o obt,ain a 71% yield of 6-(methylamino)heptanol. ,V-Methyl-2-phenylpropylamine,cinnamaldehyde, and 98% formic acid were refluxed to get N-cinnamyl-N-methyl-2-phenylpropylamine, a biologically active compound, b y Shelton ( M ) . Tield was not stated.
PREPARATION OF NITRILES The commercial production of nitriles is of much interest at the present time. Drew and Funderburk (29-31) improved the preparation of fatty acid nitriles, by reaction between fatty acids and ammonia, by employing soluble cittalysts to render the reaction mixture homogeneous. They patented reacting higher fatty acids, tall oil, and rosin in liquid phase with gaseous ammonia in the presence of a strontium, calcium, or zinc salt (Group I1 of the periodic table) of these acids at about 260" t o 350" C. Simplified equipment is used. MacLean and Pickart ( 6 8 ) secured patent protection for producing aliphatic nitriles by passing a gaseous mixture of saturated aliphatic carboxylic acid and ammonia over a fluidized alumina catalyst at 300' to 400" C. Acetic acid led to acetonitrile in 93% conversion per pass and to a n efficiency of conversion of 97%; and 0.52 part by weight of this product was obtained per hour per part by weight of catalyst. I n manufacturing nitriles from fatty acids with ammonia and fractionating the products in a vertical zone, Williams (112) patented the improvement of passing gaseous ammonia upward through the heavy nit,rile fraction to strip out light nitriles and other low boiling impurities. Mayurnik et al. ( 7 4 ) studied, in an exploratory manner, the vapor phase catalytic reactions of alkylpyridines. I n general, the elements of Groups V, VI, and VI11 of the periodic table yielded nicotinonitrile. Reaction products were cyanopyridines and pyridinecarboxamides. p-Picoline gave a 60% yield of nicotinonitrile using Harshaw vanadium catalyst at 310" C. Denton and Bishop (28) obtained a patent on producing isonicotinonitrile by contacting ?-picoline with ammonia in gaseous phase in the presence of a molybdenum oxide catalyst a t about 540' C. The example shows 1.5% by weight conversion of the picoline to isonicotinonitrile per pass. A British patent to the Pocony-Vacuum Oil Co. ( 9 4 ) shows the vapor phase react'ion
Vol. 45, No. 9
of ammonia with alkylated aromatic compounds, alkyl heterocyclics, alkylthiophenes, olefins, primary alcohols, and glycols. Vanadium, molybdenum, and tungsten oxides, molybdic acid salts, and nickel salts are used. Pyridium Corp. ( 8 4 ) prepared cyanopyridines by passing alkylpyridine vapors, excess ammonia, and air a t 300" to 375' C. over various catalysts in a stainlese steel tube. Using ferric vanadate catalyst, 3-methylpyridines gave 3-cyanopyridine.
CYCLIZATIONS Many references have appeared in 1952 on cyclizing reactions. Iloog and Engel (45,46) obtained patents on preparing 3-picoline, a n intermediate for nicotinic acid. Allyl alcohol plus excess ammonia and nitrogen were passed through a reactor containing alumina-copper catalyst a t 300' to 500' C. and atmospheric pressure. Ishiguro et al. (62) studied the formation of pyridine bases, 2-picoline particularly, from acetylene and ammonia. The best catalyst was cadmium phosphate which increased the yield of 2-picoline and decreased the yield of acetonitrile. Alkylpyridines have been prepared by Mahan (70) by interacting a ketone or aldehyde with ammonia in the presence of a fluorine-containing catalyst. 5-Ethyl-2-methylpyridine was obtained from paraldehyde and ammonia in the presence of aqueous hydrogen fluoride a t 260" C., the yield being 73%. Leditschke ( 6 2 ) svnthesized 3-hydroxyl-2-arylpyridines from phenyl 2-fury1 ketones. 3-Hydroxy-2-phenylpyridine was prepared in 59% yield by heating phenyl 2-fury1 ketone with ammonium acetone for 10 hours a t 250' C. Weiss (107) extended an improved Chichibabin synthesis t o the making of arylated pyridines. The medium consists of acetic acid containing ammonium acetate. I n the case of sluggieh reactions the acetic acid is replaced by acetamide. A mechanism is proposed for formation of the pyrldine ring. Yields of phenylated pyridines were up to 68%. Aliphatic aldehydes react with aldimines to form 1,2,3,5tetraalkyldihydropyridines and hr-all~enylidenealk~~lamines accoiding to Patrick (79). The dihydropyridines n cre hydrogenated to piperidines. Schrcyer (91) found t h a t 3,3-dialkylpiperidines can be synthesized from 2,2-dialkyl-4-cyanobutyraldehyde by hydrogenation in the presence of ammonia and Raney nickel a t about 110" to 130" C. and 700 atmospheres pressure. &--Substituted piperidines, pyrrolidines, and morpholines have been made in moderate yields by Reynolds and Kenyon ( 8 7 ) by condensing primary amineb iTith disulfonates of glycols. Bourns et al. ( 1 0 ) obtained around 90% yields of 1-arylpiperidines by the vapor phase reaction of tetrahydropyran and aniline or 0-, m-, and p-toluidines over activated alumina catalyst. Copenhaver (24) produced 2-quinolines by reacting a primary aromatic amine with a 1,1,3-trialkoxy-3-substitutedpropane under anhydrous conditions in the presence of an acid catalyst. A 55% yield of quinaldine resulted from heating aniline with 1,1,3-trimethoxybutane and a catalytic amount of ammonium chloride. l-Substitute$-6,7-dialkoxy-1,2,3,4-tetrahydroisoquinolines were obtained in 90% yields by Lepape ( 6 3 ) . An aldehyde was condensed with a phenylethylamine to an imine followed by subsequent cyclization by heating with 85% orthophosphoric acid plus a trace of hydrogen chloride. The process can be carried out in one step. Bordner (8) patented an improved process for preparing p j r roles. Furans or tetrahydrofurans in the vapor phase are heated with ammonia or primary amines and steam in the presence of an alumina dehydration catalyst. Conversions and yields ranged up to 63 and SO%, respectively. de Benneville and Strong (3) obtained insecticidal pyrrolidines from reacting a mono- or dlprimary amine with acetonyl-acetone and hydrogen cyanide in the presence of-e.g., piperidine, as a catalyst. Kiprianov et al. (56) reacted o-amino-thiophenol with diethyl malonates in carbon dioxide a t about 200" C. to obtain dibenzo-
September 1953
I,
INDUSTRIAL AND ENGINEERING CHEMISTRY
1919
thiazolylmethanes. Yields were 60 to 95y0. Gunther (40) condensed 2,4-diaminoanilines with a lower alkyl a-keto-carboxylic acid or alower alkyl aldehyde to dihydrobenzimidazole type products of interest in photographic work. Yields were in the range of 60 to 70%. A 70% yield of 3-morpholone resulted from reacting ethanolamine, sodium, and ethyl chloroacetate by Vieles and Seguin (106). Ethyl a-bromopropionate was also used. Reck (86) patented a process for preparing N-aliphatic morpholines by cyclizing bis(2hydroxyethyl) aliphatic hydrocarbon amines in vapor phase a t 300" to 400'C. in contact with a dehydration catalyst; the yields varied upward to about 80%.
formamido groups, and then hydrolyzing the latter to amino groups. Improved melamine resins for use as anion exchangers have been made by Lundberg (65)by treating an aliphatic polyamine with triethylenemelamine.
PREPARATION OF QUATERNARY AMMONIUM COMPOUNDS
Some of the primary amines reacted with two parts of propiolactone to form the corresponding tertiary amine. p-Toluidine gave both the acid above and an amide. These reactions are not catalyzed by sodium ethoxide or sulfuric acid. Yields were about 50 to 90%. Bortnick ( 9 ) heated 75 to 25 mole yoof urea and 25 to 75 mole % of a tert-alkylamine a t 100" to 150' C. until cessation of ammonia liberation and then heated the product to 180' t o 250' %. to get a tert-alkyl isocyanate. Conversions were about 30 to 40%. Marsh (72) claimed patent protection on preparing guanidine thiocyanate by passing ammonia and carbon bisulfide into molten guanidine thiocyanate a t about atmospheric pressure and about 200 O to 220 c. Flenner (57) developed an improved method for making salts of alkylene bis-dithiocarbamic acids by first forming an intermediate product by adding carbon disulfide gradually with agitation to an alkylenediamine and then without separating the intermediate, the latter is reacted with an hydroxide of sodium, lithium, potassium, magnesium, or calcium, the steps being a t not over 50" C., and preferably in presence of water. In an example, 17.9 parts of ethylenediamine, 45.3 parts of carbon disulfide, and 23 parts of calcium hydroxide led to 75 parts of calcium ethylene bisdithiocarbamate. Gilman, Zarember, and Bee1 (58) investigated the cleavage of 2-benzyloxyquinoline by some aliphatic amines, aromatic amines, and amides. Organosilyl amides were prepared by Sommer (95). For instance, p-trimethylsilylpropionyl chloride was treated with an ether solution of anh drous ammonia a t -70' C., trimethylsilylpropionamide being Zrmed. Erickson (34) reacted primary alkylamines, dialkylamines, bis(hydroxyalky1)-amines and piperidine with hydrogen cyanide a t about 15' to 75' C. t o obtain N-substituted formamidines.
There has been considerable interest in 1952 concerning quaternary ammonium compounds. The preparation of synthetic choline chloride, which is a vitamin additive in animal and poultry feeds, has been patented by Klein and Kapp (57). Ethylene chlorohydrin and 25% aqueous trimethylamine were reacted exothermically to give choline chloride in substantially quantitative yield. Hey (44) prepared aryloxycholine bromides from aryloxyethyl bromides and anhydrous trimethylamine in acetone at room temperature. Hartmann and Bosshard ( 4 1 ) patented disinfectants-i.e., pphenoxyethyl-dimethyl-dodecyl-ammonium halides-which were made in good yield from the reactant amine and dodecyl halide. Britton and Hansen ( l a ) obtained patent coverage for parasiticidal picolinium compounds. In one example, equimolar amounts of 2- [2-(2,3,4,6-tetrachlorophenoxy)ethoxy]ethyl chloride and pyridine were heated a t 98' t o 100" C., giving an 80y0 crude yield of the expected pyridinium chloride. Niederl, Niederl, and McCreal (77) prepared bactericidal N-alkyl-N-p-alkoxyethyl morpholinium alkyl sulfates by reacting morpholylethyl alkyl ethers with dimethyl sulfate. A patent to Robinson and Cusic ( 8 9 ) covers new 10-(quaternary ammonium alky1)phenothiazine salts.
ION EXCHANGE RESINS McBurney (66) has patented insoluble anion exchange resins obtained by reacting a halomethylated copolymer of styrenes and divinylbenzene with a primary or secondary amine such as polyethylene polyamine a t about 80' t o 100' C. Bodamer ( 7 ) obtained patent coverage on making anion exchange resins from chloromethylated styrene-butadiene copolymer and a primary or secondary amine. Bauman and McKellar ( 8 ) have prepared water-insoluble anion exchange resins from halomethylated copolymers of styrene and divinylbenzene with tertiary amines. McMaster ( 6 9 ) patented a method of making quaternary ammonium anion exchange resins in the form of spheroids by halomethylating a benzeneinsoluble copolymer of styrene and divinylbenzene and a halomethyl methyl ether in presence of perchloroethylene to swell the copolymer and then reacting with a tertiary amine. Phenol-aldehyde-?mine anion exchange resins were obtained by Braithwaite and D'Amico ( 1 1 ) by reacting a polyalkylene polyamine with formaldehyde or furfural and then with phenol. Stroh ( 9 8 )has patented a combination of anion active resin from an alkylenepolyamine with epichlorohydrin and a cation active resin which is a nuclear sulfonated phenol-aldehyde condensation product. The manufacture of an anion exchange resin by the condensation of an alkylenediamine with acetone and formaldehyde is the subject of a patent t o Whittaker and Allen (108). Skogseid (93) obtained cation exchange resins by condensing a polyaminostyrene with a nitrated halobenzene and then nitrating the benzenoid ring structure with excess nitric acid. Hwa (51) prepared anion exchange resins by proliferously 'polymerizing methyl vinyl ketone with a polyolefinic compound, reacting the keto groups with formic acid and triethylenetetramine to get
MISCELLANEOUS Propiolactone was found by Hurd and Hayao (48) to react with aniline derivatives to form acids as follows: YC8HnNHz
+ CHzCHzC=O -0--1
Y representing -COOH, and Not.
+
-COOEt,
YCeHJTHCHzCHzCOOH
-SOJI,
-SOzNH,,
C1, Br,
-
LITERATURE CITED (1) Armitage, J. B., and Whiting, M. C., J. Chem. SOC.,1952, 2005. (2) Bauman, W. C., and McKellar, R. (to The Dow Chemical Co.), U. S. Patent 2,614,099 (Oct. 14,1952). (3) de Benneville, P. L., and Strong, J. S. (to Rohm & Haas Co.), Ibid., 2,580,738 (Jan. 1, 1952). (4)Bergmann, E. D., and Lavie, D., J . Am. C h m . Soc., 74, 4948 (1952). (51 Bestian. H. (to Farbewerke Hoechst vorm. M.L.B.). TJ. S. Pate& 2,596,200 (May 13,1952). (6) Bieber, P., Compt. rend., 234,1783 (1952). (7) Bodamer, G. W. (to Rohm & Haas Co.), U. S. Patent 2,597.439 (May 20,1952). (8) Bordner, C. A. (to E. I. du Pont de Nemours & Co.), I b i d . , 2.600.289 (June 10. 1952). (9) Bortniok, N. M. (to Rohm & Haas Co.), Ibid., 2,611,782 (Sept. 23,1952). (10) Bourns, A. N., Embleton, H. W., and Hansuld, M. K., Can. J . Chem., 30,l (1952). (11) . . Braithwaite. D. G., and D'Amico. J. S. (to National Aluminate Corp.), U. S. Patent 2,582,098 (Jan. 8,1952). (12) Braunholtz, J. T., and Mann, F. G., J. Chern. SOC.,1952,3046. (13) Britton, E. C., and Hansen, J. N. (to The Dow Chemical Co.), U. 8. Patent2,621,185 (Dee. 9,1952). (14) Burke, W. J., Xobezen, M. J., and Stephens, C. W., J . Am. Chem. SOC.,74,3601 (1952). (15) Burke, W. J., Smith, R. P., and Weatherbee, C., Ibid., 74, 602 (1952). (16) Burke, W. J., and Stephens, C. W., Ibid., 74,1518 (1952). (17) Butler, G. B., and Goette, R. L., I b i d . , 74,1939 (1952). (18) Caldwell, J. R. (to Eastman Kodak Co.), U. S. Patent 2,618,658 (Nov. 18.1952). (19) Charpentier, P'. (to Soc. des Usiiies Chim. RhGne-Poulenc), Ibid.,2,595,215 (May 6,1952). \-I
1920
INDUSTRIAL AND ENGINEERING CHEMISTRY
(20) Clifford, A. M. (to Wingfoot Corp.), Ibid., 2,615,892 (Oct. 28, 1952). (21) Cocker, W., Cross, B. E., and McCormick, J., J . Chem. SOC., 1952,1182. (22) Cook, E. W., and Moss, P. H. (to Am. Cyanamid Co.), U. S. Patent 2.589.674 (March 18. 1952). (23) Copenhaver, J. W. (to General Aniline &- Film Corp.), Ibid., 2,593,853 (April 22, 1952). (24) I b i d . , 2,608,557 (Aug. 26, 1952). (25) Craig, W. E., and Exner, L. J. (to Rohm & Haas Co.), Ibid., 2.613,226 (Oct. 7,1952). (26) Davies, P., Reynolds, P. W., Coats, R. R., and Taylor, ,4. W. C. (to Imp. Chem. Ind., Ltd.),I h i d . , 2,609,394 (Sept. 2, 1952). (27) Deanesly, R. bl. (to Universal Oil Products Co.), I h i d . , 2,583,729 (Jan. 29,1952). (28) Denton, W. I., and Bishop, R. B. (to Socony-Vacuum Oil Co ), Ibid., 2,592,123 (April 8, 1952). (29) Drew, J., and Funderburk, J. C. (to Hercules Powder Co.), Ibid., 2,589,232 (March 18, 1952). (30) I b i d . , 2,589,233 (March 18, 1952). (31) I b i d . , 2,590,072 (March 18, 1952). (32) Eliel, E. L., and Anderson, R . P., J . Am. Chem. SOC.,74, 547 (1952). (33) Erickson, J. G., I b i d . , 74, 6281 (1952). (34) Erickson, J. G. (to American Cyanamid Co.), U. S. Patent 2.615.023 (Oct. 21. 19521. , . . (35) Ferrero, P., et al. (to Socii36 Carbochimique, Societe dnonyme), Ihid., 2,622,073 (Dee. 18, 1952). (36) Ibid., 2,622,099 (Dec. 16, 1952). (37) Flenner, A. L. (to E. I. du Pont de Nemours & Co.), I b i d . , 2,609,389 (Sept. 2, 1952). (38) Gilman, H., Zareniber, I., and Beel, J. A , , J . Ana. Chem. SOC., 74,3177 (1952). (39) Gruber, W., Heckmaier, J., and Reinecke, H. (to R. Decker and H. Holtz), Ger. Patent 807,207 (June 25, 1951). (40) Gunther, R. C. (to General Aniline & Film Corp.), U. S. Patent 2,605,265 (July 29, 1952). (41) Hartmann, M , , and Bosshard, W. (to Ciba Pharmaceutical Products, Inc.), Ibid., 2,581,336 (Jan. 8, 1952). (42) Hartough, H. D., and Dickert, J. J., Jr. (to Socony-Vacuum Co.), Ibid., 2,582,867 (Jan. 15, 1952). (43) Heider, R. L. (to AIonsanto Chemical Co.), I b i d . , 2,603,660 (July 15, 1952). (44) Hey, P., Brit.J . Pharmacol.,7,117 (1952). (45) Hoog. H.. and Eneel. F. W.(to Shell Development Co.), Ibid., 2,603,845 (July 75,1952). (46) Ibid., 2,605,264 (July 29,1952). (47) Hopff, H., and Spanig, H. (to Badische Anilin- & Soda-Fabrik), Ger. Patent 840,546 (June 3,1952). (48) Hurd, C. D., and Hayao, S., J . Am. Chem. Soc., 74,5889 (1952). (49) Hurwita, M. D. (to Rohm & Haas Co.), C. S.Patent 2,582,128 (Jan. 8,1952). (50) Huscher, &I. E., Long, M. W., Jr., and Moore, J. C. (to The Dow Chemical Co.), Ibid., 2,602,819 (July 8, 1952). (51) Hwa, J. C. H. ( t o Rohm & Haas Co.), Ibid., 2,597,491 (May 20,1952). (52) Ishiguro, T., Itaya, hl., Kubota, S., and Tabata, S . ,J . Pharm. SOC. J a p a n , 72, i l l (1952). (53) Ishiguro, T., Kitamura, E., Kubota, S., and Tabata, N., Ibid., 607 (1952). (54) Jones, E. M. (to Parke, Davis and Co.), U. S. Patent 2,582,257 (Jan. 15,1952). (55) Jones, G. D. (to General Aniline & Film Corp.),IbLd., 2,593,888 (April 22, 1952). (56) Kiprianov, A. I., et al., Zhur. Obshchei Khim., 22, 302 (1952). 1571 Klein. H. C.. and Kaao. R. (to Nopco Chemical Co.), U. S. Patent 2.623.901 fDec.'30. 19521. (58) Kozlov, N: S.;and Akhmetshima, L., Doklady A k a d . N a u k S.S.S.R., 85,91 (1952). (59) Kratzl, K., and Kvasnicka, E., M o n a t s h . , 83, 18 (1952). (60) Kurtz, P., and Schwarta, H . (to Farbenfab. Bayer), Geiman Patent 830,190 (Jan. 31,1952). (61) La Forge, R. A., Whitehead, C. R., Keller, R. B., and Hummel, C. E., J . Org. Chem., 17,457 (1952). (62) Leditschke, H., Chem. Ber., 85,202 (1952). (63) Lepape, P. A., C o m p t . rend., 234,1175 (1952). (64) Logan, A. V., and Schaeffer, W.D., J . Ant. Chem. SOC.,74,5538 (1952). (65) Lundberg, L. A. (to American Cyanamid Co.), C. S. Patent 2,620,315 (Dee. 2, 1952). (66) McBurney, C. H. (to Rohm & Haas Co.), Ibid., 2,591,574 (April 1,1952). (67) McCraoken, J. H. (to Socony-Vacuum Oil Co.), Ihid., 2,584,278 (Feb. 5,1952). (68) MacLean, A. F., and Pickart, D. E. (to Celanese Corp.), I b i d . , 2,590,986 (April 1,1952). ~I
~I
Vol. 45, No. 9
(69) McllIaster (to Dow Chem. Co.), Ibid., 2,616,877 (Nov. 4,1952). (70) LIahan, J. E. (to Phillips Petroleum Co.), I b i d . , 2,615,022 (Oct. 21, 1952). (71) LIalinovskii, M. S., and Baranov, S.N., Zhur. Priklad. Rhim., 25.410 (19523. (72) Marih, N.'H. (io ilmerican Cyanamid Co.), U. S. Patent 2,615,044 (Oct. 21,1952). (73) hlathes, R. A. (to B. F. Goodrich Co.), Ibid., 2,608.575 (Aug26,1952). (74) Mayurnik, G., et al., IKD. ENG.CHEM..44.1630 (1952). (75) Mueller, W. (to Ciba, Ltd.), U. S. Patent 2,615,917 (Oct. 28, 1952). (76) Naylor; BI. A . , Jr. (to E. I. du Pont de Nemours & Co.), I b i d . , 2,610,980 (Sept. 16, 1952). (77) Niederl, J. B., Siederl, V., and McGreal, M.E. (to J. B. K e der1 and Associates, Inc.), I b i d . , 2,581,285 (Jan. 1, 1952). (78) Nylander, R. (to Centralbolaget for Kem. Ind. Akt.). Swed. Patent 133,694 (Sov. 27,1951). (79) Patrick, T. hI., Jr., J . Am. Chem. SOC.,74, 2984 (1952). (80) Phillips, A. P.,Ibid., 74,4320 (1952). (81) Pietrusza, E. W. (to Allied Chemical and Dye Corp.), U. 8. Patent 2,580,832 (Jan. 1, 1952). (82) Pigulevskii, G. V., and Kuranova, I. L., Dokladu Akad. S a u k . S.S.S.R.,82, 601 (1952). (83) Pollard, C. E., and T. H. Wicker, J . Org. Chem., 17, 1 (1952). (84) Pyridium Corp., Brit. Patent 671,763 (May 7, 1952). (85) Raczynski, W. A. (to Hercules Powder Co.), U. S. Patent 2,615,918 (Oct. 28, 1952). (86) Reck, R. A. (to Armour and C o . ) , Ihid., 2,597,260 (May 20, 1952). (87) Reynolds, D. D., and Kenyon, W. 0. (to Eastman Kodak Co.), Ibid., 2,581,443 (Jan. 8, 1952). (88) Ring, H. R., and Ormerod, W.E., J . Pharm. a n d Phaimacol., 4,21 (1952). (89) Robinson, R. A., and Cusic, J. W.(to G. D. Searle and Co.), U. S.Patent 2,590,125 (March 25, 1952). (90) Roe, E. T., Stutzman, J. M., Scanlon, J. T., and Swern, D., J . Am. Oil Chemists' SOC., 29.18 (1952). (91) Schreyer, R. C., J . Am. Chem. Soc., 74,3194 (1952). (92) Shelton, R. S. (to Wm. S.Merrell Co.), U. S.Patent 2,595,372 (Mav 6.1952). (93) Skogseid, (to'Norsk Hydro-Elektrisk Kvaelstofaktieselskab). Ibid., 2,592,350 (April 8 , 1952). (94) Socony-Vacuum Oil Co., Brit. Patent 664,832 (Jan. 16, 1952). (95) Sommer, L. H., (to Dow Corning Corp.), U. 8.Patent 2,610,198 (SeDt. 9.1952). (96) Sprules, F. J., and Bell, J. B. (to Kopco Chem. Co.), Ibid., 2,608,584 (Aug. 26, 1952). (97) Stichnoth, 0. (to Badische Anilin- & Soda-Fabrik), Ger. Patent 830,047 (Jan. 31,1952). (98) Stroh, G. R. (to American Cyanamid Co.), U. S.Patent 2,586,882 (Feb. 26,1952). (99) Stuhmer, W., and Kauptmann, W.,Arch. Pharm., 285, 120 (1952). (100) Suter, H., and Zutter, H., Snn., 576,215 (1952). (101) Swern, D., and Findley, T. W., J . Am. Chem. Soc., 74, 6139 (1952). (102) Takatori, K., and Ueda, M., J . Pharm. SOC.J a p a n , 71, 1375 (1951). (103) Teter, J. W., and Olson, L. E. (to Sinclair Refining Co.), U. S. Patent 2,623,061 (Dec. 23, 1952). 1104) TStaineer. G. E.. Helv. Chim. Acta. 35.1359 (1952). (105j Vaughan; R. %,'and Bean, F. R. (to Eastman Ko'dak Co.), U. S. Patent 2,618,657 (Nov. 18, 1952). (106) Vieles, P., and Seguin, J., C o m p t . rend., 234, 1980 (1952). (107) Weiss, M., J. Am. Chem. Soc., 74, 200 (1952). (108) Whittaker, D., and Allen, G. G. (to Imperial Chemical Industries, Ltd.), U. S. Patent 2,588,784 (M&h 11, 1952). (109) Wilder. R. S.. and Herman. D. F. (to Publicker Industries. Inc.j, Ibid., 2,580,494 (Jan. 1, 1952): (110) Wiley, P. F., J . Am. Chem. SOC., 74,4326 (1952). (111) Wiley, P. F. (to Eli Lillyand Co.), U. S. Patent 2,621,189 (Dee. 9, 1952). (112) Williams, G. B. (to A I . W.Kellogg C o . ) ,Ibid., 2,616,838 (Nor. 4, 1952). (113) Williams, W. W., and Strobel, A. F. (to General Aniline & Film C o r p . ) , I b i d . , 2,619,502 (Nov. 25, 1952). (114) Winsten, W. A. (to Food Research Laboratories, Inc.), Ibid., 2,614,104 (Oct. 14, 1952). (115) Wissow, L. J. (to AIerck and Co.), Ibid., 2,617,805 (Kov. 11,
A.
19.52).
(116) Wolff, V., Ann., 576, 35 (1952). (117) Wright, H. J., and Cramer, A. B. (to a4ssoc. Am. Soap and Glycerine Producers), U. S. Patent 2,618,659 (Nov. 18,1952). (118) Wright, J. B., and Lincoln, E. H., J . Am. Chem. SOC.,74, 6301 (1952).
