INDUSTRIAL AND ENGINEERING CHEMISTRY
1846 SULFITE REDUCTIONS
(1F) Goldblum. K. B., and Montonna, R.E., J . Org. Chem., 13, 17985 (1948). MISCELLANEOUS REDUCTIONS
Bean, F. R. (to Eastman Kodak Co.), U. S. Patent 2.446.519 (Aug. 10, 1948). Bredereck, H., and von Schuh, H., Chem. Ber., 81, 215-21 (1948).
Dewing, T., and Dyke, W. J. C., British Intelligence Objectives Sub-committee, London, BIOS Final Rept. 306 (1946). Ghielmetti,G., Farm. sci. e tec. (Pavia),3,51-2 (1948). Gluck, B., U. S. Dept. of Commerce, Washington, D. C., OT6, FIAT Final Rept. 943 (1947).
Hodgson, H. H., and Dixon, S., J. Chem. SOC.,1948,1714-15. Ino, K., and Oda, R., J. SOC.Chem. Ind. Japan, 46, 552-3 (1943) Ibid., pp. 1182-3. I
Bs ARTHUR C.STEVENSON, DE NEMOURS
Vol. 41, No. 9
(9G) Jain, B. C., Mirohandani. P., Iyer. B. H., and Guha, P o e.. J . Indian Chena. SOC.,24,191-2 (1947). OOG) Krueger, J. (to Edwal Laboratories,Inc.), U. S. Patent 2,461,498 (Feb. 8, 1949). (11G) Lockemann, G., and Kegler, H., Chem. Ber., 80,479-84 (1947). (12G) Nystrom, R. F.,and Brown. W. G.. J . A m . Chem. SOC..70 3738-40 (1948). (13G)Pascual, J. A., British Patent 607,490 (Aug. 31, 1948). (14G) Romeo, A., Ricercu sci. e ricostruz., 18, 1057-8 (1948). (15G) Smith, L. I., and Opie, J. W., Org. Syntheses, 28, 11-13 ( 1 9 4 8 ~ ~ (16G) Sorm, F., and Brandejs, J., Collection Czech. Chem. Communs., 12, 444-54 (1947). (17G) Uffer, A., and Schlittler, E., Helu. Chim. Acta, 31, 1397-14001 (1848). (18G) Ward, Blenkinsop and Go., Ltd., and Goldberg,A. A., Britie'b Patent 602,231 (May 25, 1948). (19G) Weizmann, M.. Israelashvili, S., and Papo, R., J . Am. C R m SOC.,70, 4263-4 (%94S), RECEIVED June 16, 1949.
AM MON OLYSI E. I. DU PONT
C O M P A N Y , INC., W I L M I N G T O N , DEL.
T
HERE have been numerous applications of the unit process ammonolysis during the past year. Much of the work has been concerned with expanding and improving well established applications-for example, reactions of ammonia with acids, aldehydes, alcohols, esters, olefins, and substituted unsaturated compounds. Improvements have been made in controlling the nature of the reaction leading to specific products. Some attention has been given to development of new catalysts, ammonia recovery, and isolation of the products of the reaction. A new development is found in the manufacture of nitriles directly from paraffinic and aromatic hydrocarbons. This novel etdvance has been contributed by Denton, Bishop, Marisic, Caldwell, and Chapman of the Socony-Vacuum Oil Company, with their procedure for manufacture of nitriles by the direct combination of hydrocarbons and ammonia. The reaction is effected in the vapor phase a t approximately 1000 I?. in the presence of a catalyst composed of one or more of the oxides of tungsten, molybdenum, or vanadium, preferably supported on alumina. For tlue purpose of discussion this unit process has been divided into a number of sections according to starting materials. O
Ammoniaandhydrocarbonin the molar ratio of 2 to 1pass through the catalyst chamber with an average contact time of 4 seconds. The products are condensed from the unreacted material and are fractionally distilled. While a number of cycloparaffinic matepi. a1s have been used as feed stocks, those containing methyl groupr are preferred-for example, methyl and dimethyl cyclohexane. In most cases, there is some cleavage of carbon t o carbon bonds during the reaction. This cleavage leads to nitriles containing fewer carbon atoms than the starting materials. The products resulting from the ammonolysis of several different starting paraffinic materials are shown in Table I.
A R O M A T I C HYDROCARBONS Application of this technique to the direct reaction of alkyl aromatics with ammonia has led to practical processes for the manufacture of benzonitrile, tolunitrile, and xylonitrile according to the following equation:
0 CN
CH,
-'
825' to 1075' F.
HI IiHr MoOa.P2Oa.A1~Oa * PARAFFINS " " Past practice in the manufacture of aliphatic nitriles has involved reactions of ammonia with olefins, aldehydes, or aliphatic This simple one-step procedure is in marked contrast t o the acids in the presence of appropriate catalysts frequently consistformer methods of preparation of aromatic nitriles-namely, the reaction of aromatic halides or sulfates with alkali cyanides; the ing of various forms of cobalt, manganese, or chromium supported on silica or alumina. The reaction of ketones with hydrodecomposition of diazonium halides with potassium cuprow cyanide; or the decomposition of isothiocyanates with copper OK gen cyanide in the presence of a dehydration catalyst likewise leads to nitriles. Marisic et al. (344)have, devised a new procedure zinc dust. involving a direct vapor phase reaction of paraffinic or cycloTable 1. Products of Ammonolysis of Paraffinic Hydrocarbons paraffinic hydrocarbons with Product Wt. % Conversion per ammonia in the presence of a PASS Based on HC NHs/HC, Contaot catalyst made up of one or Molar Time, ScetoBenaoToluPropioCatalyst Ratio Sec. nitrile nitrile nitrile nibrile more of the oxides of molybdenum or tungsten. The reacCycloparaffin Stocks Methylcyclohexane (20) 20% Moos, 80% AlzOs 2 : 1 2.5 1.6 1.5 ... .. tion is effected a t a temperaDimethylcyclohexane 20% M O O S ,SO% Altos 2:1 5.0 0.5 ... 1.8 (10) ture of approximately 1000° F. 0 . 5 (mixed aromatic nit,riled Methylcyclopentane (14) 20% VzOs, SO% Ala03 2:1 2.5 1 .O in a reactor consisting of a shell containing a catalyst chamber Propane (16) 20% VzOa 80'7 AI& 2:l 4.0 3.6 ... ... ... ... Butane (16) 20% Vzos: Sod AlzOs 2:1 4.0 3.0 heated with a heat transfer Heptane (fa) Moos, WOs, AlzOs 2.7:1 0.9 0.5 3:O ... i:4 medium from outside the shell. "
j
.
INDUSTRIAL AND ENGINEERING CHEMISTRY
September 1949 Table 11.
Eydrocarbon Toluene ($8) Xylene ($41) Trimethylbenzene (6)
Table 111.
U
lo% MoOa, 90% All01 (6)
Vios,AliOa (18) MOOS,Pzoo,AliOa (83)
Li uid Molar Ratio, Temp., OF. Space %elocity NHI/HC 2.3:l 975 3 1 2,0:1 965 3:4 1.9:l 979 3.0
Liquid Spape Velocity/
Hour
3.11
0.90
3.1
Molar Ratio
Vol.
% of
Charge/ NHdH'C Pass 2 . 3 :1 6.8 2 :1 5.4 2.3:l 9.0
Product Benzonitrile Benzonitrile Benzonitrile
The catalysts consist of oxides of phosphorus, molybdenum, or tungsten supported on alumina. Tungsten oxide is found far less effective than molybdenum oxide, which is the preferred catalyst. A summary of the operating conditions is included i n Table 11. The relative efficiencies of the several metal oxide catalyst combinations are given in Table 111. The combination of the oxides of molybdenum and phosphorus supported on alumina is the most effective.
OLEFINS AND SUBSTITUTED UNSATURATED MOLECULES Application of the techniques developed by the investigators at Bocony-Vacuum Oil Company for ammonolysis of hydrocarbon materials was extended also to olefinic charging stocks. While the ammonolysis of ethylene yields only acetonitrile, the use of olefins containing more than two carbon atoms leads to by-products resulting from carbon t o carbon fission. For example, acetonitrile is obtained from propylene, ethylene, and butadiene in yields of 16 t o 32% per pass. This yield is based on the weight of the starting hydrocarbon charged (11). The following reactions obviously compete in the ammonolysis of propylene :
+ NHo + CHaCHzCN + 2Hn C H r C H = C H s + Hz ----t CHaCHzCHa CHaCHt-CH: + NHs + CHoCN + CH, + 2H1 CHaCH2CrU' + H, + CHiCN + CH, CHo-CH=CH,
R
denum, phosphorus, vanadium, tungsten, and silica, sup% Converaion, ported on alumina. A catalyst Based on composed of 20% vanadium Wt. % HC Charged Product pentoxide and 8@%alumina is 9.0 Beqzonitrile found more effective than one 10.0 Tolunitrile 8.6 Xylonitrile composed of 10% vanadium pentoxide and 90% alumina. The catalyst is prepared by repeatedly soaking the support in a solution of a soluble salt of the desired metal, followed by decomposition at approximately 1000" F. (16). Teter (67)has contributed a simple method for the recovery of ammonia from this type of system containing mixtures of alkanes and alkenes-for example, propane, propylene, and ammonia. The procedure involves cooling the mixture to approximately 0" F. under sufficient pressure to establish liquid phase conditions and separating the ammonia and hydrocarbon layers. The lower ammonia layer containing about 270 hydrocarbon material is of satisfactory quality for re-use without further purification. The hydrocarbon layer contains approximately 2% ammonia. Before this separation can be made it is necessary to condense the g products of the reaction from the reaction va-
Reaction Data for Aromatic Nitrile Manufacture
Relative Effectiveness of Catalysts in Ammonolysis of Toluene Yield,
Catalyst r
1847
The products actually isolated include a trace of propionitrile and a 32% yield per pass of acetonitrile. The yield is based on the weight of the hydrocarbon charged. With the use of butadiene, the product includes acetonitrile, propionitrile, and butyronitrile. Acetonitrile is the principal product (21). A higher ratio of ammonia increases the yield of acetonitrile and essentially eliminates the by-products. A similar procedure (91) using a 3 to 1 ammonia-propylene molar ratio over an aativated alumina catalyst (with a space velocity of 160 per hour eLnd temperatures of 1150' to 1200' F.) leads to a 32% yield, based on propylene, of acetonitrile. Lower yields of acetonitrile are obtained with isomeric butenes. The use of a small amount of moisture in a n ethylene and ammonia reaction mixture is reported (8) to give nearly theoretical yields of acetonitrile. A slightly alkaline catalyst composed of alumina (3574, zinc oxide (61.85%), chromic anhydride (3%), and sodium hydroxide (0.15%) is used at temperatures of 300" t o 500" C. Olefins with more than six carbon atoms undergo aromatization during the reaction with ammonia-for example, octene yields benzonitrile and a trace of acetonitrile (16). Catalysts include various combinations of the oxides of molyb-
BUGand Ford (4) have obtained P-aminopropionitrile as the principal product and di(cyanoethy1)amine as a by-product, by reacting acrylonitrile with aqueous ammonia at 90 a to 100 O C. Higher ammonia molar ratios favor primary amine formation. For example, a 10: 1 molar ratio of ammonia to acrylonitrile results in a 78.3% yield of the o-aminopropionitrile and 21.7% di(cyanoethyl)amine, whereas with a 3 t o 2 ratio the product is composed of 63.1% primary amine and 36.9y0 secondary amine. These yields are based on the starting acrylonitrile. Acrylonitrile reacts also with allylamine a t 135' C. to give good yields of 8-allylaminopropionitrile (80). Robinson and Olin (SI)have devised a method for converting crotonaldehyde to l,3-diaminobutane by treatment with hydrogen and ammonia over a nickel-hydrogenation catalyst. The addition of ammonia to the double bond is favored over saturation by hydrogen addition by using a 10 to 1 molar ratio of ammonia to aldehyde and controlling the rate of addition of the aldehyde to the other reactants under reaction conditions. Methanol is used as a solve nthesize pyridine from acetylene and amomprising zinc chloride and an alkali metal chloride, Hanmer and Swann (%5) obtained a 60% yield, based on total weight of reactants consumed, of acetonitrile of 75 to 85% purity. Several salt systems were studied but only those containing zinc chloride were found to be effective catalysts. The reaction of allyl alcohol and ammonia over a copper catalyst supported on alumina leads to an 18%yield, based on allyl alcohol, of 3-methylpyridine. A temperature of 740' to 800'F. is t time of 2 to 3 seconds. A combination copsupported on alumina leads to a 36% yield, based on allyl alcohol (49). Alkylpyridines are made also by reacting acetaldehyde and ammonia over a silica gel-alumina catalyst a t 800' t o 950' F. Three moles of ammonia are used for each mole of acetaldehyde. The product consists of kmethylpyridine, Cmethylpyridine, and high boiling pyridines in yields of 20.40J0, 17.t370,and 10.4%, respectively, based on the starting acetaldehyde (4B). A French patent (40) claims zirconium dioxide as a catalyst for the reaction of acetylene and ammonia to form acetonitrile. Some ethylenimine is obtained in addition to acetonitrile. Rose (68)reports that acetylene reacts with ammonia, in the presence of complex salts such as Co(NH&C12, yielding kmethyl-5ethylpyridine. The reaction is postulated to involve an intermediate vinylamine, CHz=CHNH,. Aqueous trimethylamine and acetylene at 60" C. under pressure give trimethylvinylam-
INDUSTRIAL AND ENGINEERING CHEMISTRY
1848
monium hydroxide and siniilarlj trimethylviriylammoriium chloride is formed from the corresponding trialkylamnionium salt (66). The alkali metals have been used t,o proniott, the addition of amines t o unsaturated compounds. Danforth (8) hhow that primary or secondary amines react with aryl alkenes-for example, styrene-in the presence of metallic sodium, potassium, or lithium in the form of the alkali metal--amine compound. A 21% yield of 6-dibutylaminoethylbenzene based on the alkylamine, is reported in the rcaction between styrene and dibutylamine. The reaction is effected over 50 hours at 100" to 130 O C. A similar reaction is reported by Weslon (&?) in m-hich a yield of 79 to 8501,, based on the amine, of 3-(dibul3.lamino)propaii-l-o1 is obtained. Three moles of allyl alcohol, one mole of dihutylaminc, and one mole of sodium mctxl are used. Tht. reaction extends over 75 hours at 85" C. The reaction of ammonia or aniirirs u itli unsaturated cstrrs usually leads to attack of the ester group as well a$ the unsatiirated portion of the molecule. Erickson (19) has tleviscd a method for regenerating the unsaturated pnxitici,, 5-alkylacrylaniidc from the reaction product of 2 moles of a primary or secondary amine and 1 mole of a11 acrylic ester, by heating the product with a mineral acid. Sulfuric acid was found to be superior t o hydrochloric or ammonium bisulfatc. As represented by the following equation, a 74.6% yield, based on the starting ethyl acrylate, of N-n-butylacrylarriide is reportpd. II
O H
I li I CaHoS--CH&E€&' --N--C4Ha
H&O4 95-1 10" C. ' 0 fl
-
H
I n the preparation of a-alkylaminoacrylates, a similar procedure (6) involves the decomposition of methyl a-, p-di(diethy1amino)propionate at 220 O to 245 O C. to inethyl-a-diethylaminoacrylate: 0
('IT--C
/
C---OCII: I
A related applicatioii (561 which indirectly involve.; urisaturated compounds is found in the reaction of a q u e o i i ~ammonia with an epoxy group
-c
-4-
'hi
From 9,lO-epoxysteaiic acid, the corresponding 9,lO-aminohydroxystraric acid is obtained. Long chain epoxy alcohols react in a similar manner. ALDEHYDE§, ACIDS, AND ESTERS
Aldehydes continue to serve as popular starting matciials for the manufacture of amines and lower molecular weight nitriles Gresham (22, 24) has found that cobalt, or a combination of copper and zinc are specific catalysts for the manufacture of nitriles by reacting aldehydes and ammonia. For example, the reaction indicated by the, following equation results in a conversion of 777, of t h c o F > based on the starting propionaldehyde.
The chirf by-product is 2-ethyl-3,5-dimethylpyridine.This is in sharp contrast to the results obtained with the us0 of a dehydration catalyst such as alumina which gives virtually no propionitrile but appreciable quantiticss of alkylated. pyridines. The cobalt catalyst is found somewhat inferioy t o the copper-zinc com-
Vol. 41, No. 9
bination. Other cat alptic cwinbinatioiis include chromium, potassium, silica, niagnesiuni, and alumina. The catalyst is prepared by decomposition of the metallic carbonate? or oxalates followed by reduction to the free metal with dilute aqueouh methanol. Alkylamine manufacture a t the h m o n i a w e r k Meresburg G.ni.b.H. (Leuna, Germany) was carried out accordirig t o two general procedures ( 2 ) . -k. The amination of alcohols over alumina catalyst :
H. Hydroamination of aldehydes, kctcmrs, or csr'boxylic ncids according to the following scheme: RCHO
+ UHI + Ht
li was gent rally yicCtniblc to LIM the dircxct amindtron of nlcohols for producing niethyl and n-propylamine and the hydmamination of aldehydes, ketones, arid carboxylic acids for the production of several othrr aminrs. Desciiptions arid details of the processes are given for a numbtv ot the amines. Dewing and othrrs (1U ) describe dirthylaniine manufacture f i o m acetaldehyde. Thc re action is carried out with ammonia and hydrogen in a iiiolar iatio o i 1 to 1 over a nickel-chromium catalyst mhich is Statmi to have a life of 6 months. Some primary and tertiai y amines are obtained as by-products; these are recycled. The yield of diethylamine is 90 to 95y0 of theory based on the aldehyde charged. The reaction is Pffected at 120' t o 140" C. a t space velocities per hour of approximately 400. The crude is distilled by means of a bubble-cap column in stagcs, at thret. different pressures, in order to separate the three amines and unreacted ammonia. The ammonia is recovered at 15 atmospheres pressure, the primary aniine at 4 to 5 atmospheres and finally the secondary and tertiary amines are separated at atmospheric pressure. Starting with n-butgraldehyde, n-butylamine is made in a similar manner. The crude, containing 8 to 10% dibutylaminr and less than 1%tributylamine (calculatrd on the nionobutylamine yield) as well as unreacted ammonia, is fractionated by distilling first at 15 atmospheres pressure for ammonia recovery and finally at atmospheric pressure for taking off the primary amine. The secondary and tertiary amines remain behind in the still residue. Richmond et al. (60) in re-examining the system formaldehydeammonia have designated, in support of previous investigators cyclotrimethylenetriamine as the intermediate in the formation of hexamethylenetetramine. After developing a number of rate curves in studying the reaction rates relative t o ammonia and formaldehyde consumed, and product material precipitated with mercuric chloride, Boyd and Winkler (3) conclude that thc reaction is very complex. A mechanism is proposed. I n the manufacture of long chain nitriles from fatty acids, an improvement has been effected (46) which eliminates the customary steam distillation of the fatty acid residues for recovery of unreacted fatty acids. After being stripped with ammonia vltpors, in the first stage of a two-stage system, the fatty acid residues pass t o a second stage where they are stripped countcrcurrently with fresh ammonia. In this manner, the re-usable fatty acids are effectively removed and the resulting residues are discarded u7ithout further proeresing for recovery of unreacted material. The vapors resulting from this second stage pass to the first stage, where they are used in stripping the fresh fatty acid charging stock, before they are passed through the converter where the principal part of the reaction takes place. Stegemeyer (55)has found in the manufacture of unsaturated long chain nitriles that, the rate of ammonia flow through the unsaturated fatty acid markedly influences the yield of oleonitrile. The use of pressures of 30 pounds per square inch and flow rates of 0.1 liter per kilogram of stock per minute has been the usual
September 1949
INDUSTRIAL AND ENGINEERING CHEMISTRY
1849
COURTESY BOCONY-VACUUM
O I L COMPANY
Pilot Plant for Manufdcture of Aromatic Nitriles b y Ammonolysis of Aromatic Hydrocarbons
a
practice with stearic acid stocks. Pressures of 100 to 150 pounds per square inch and ammonia flow rates of 2.0 liters per kilogram per minute are found effective in reducing the amount of high boiling material and increasing the yield of the unsaturated nitrile when unsaturated charging stocks are used. A simplified procedure (48)makes use of neutral fats in place of chain nitriles are the free fatty acid. Yields of 82% claimed from saturated fatty esters, lead to somewhat lower yields. With the u it is important to distill off the unsaturated The reaction is effected at 350" C. over a dehydration catalystfor example, alumina. Free fatty acid found in the product is believed to be formed by the following mechanism. [The ammonium salt is not believed to be an intermediate in the reaction (40).1 0 2R&--NII2
0
+RCN
+ R k O H + NHa
Ammonia reacts with a diacyl derivative of 1,l-glycols in the
tures in the range of 85 O t o 100O C. and pressures of 2@00 pounds per square inch are used.
ALCOHOLS AND ETHYLENE OXIDE In the catalytic synthesis of me methanol and ammonia over an a1
n of (66)
has shown that with operating pressures in the range of 200 pounds per square inch the addition of 1 to 2 moles of water per mole of methanol prior to catalyst contact reduces the amount of tertiary amine formed t o approximately 50% of that obtained in the absence of water. It is reasoned that since the reaction is a stepwise dehydration process, the presence of water represses the ducts-that is, primary, secondary, e to the difference in the relative urn leading to the formation of the t o a greater extent. Excessive amounts of water reduced the conversion. Dixon and Cook (18) have obtained yields of 75 to 81.570, based on the starting amine, of p-alkylaminopropionitrile by reacting essentially equal molar proportions of a primary or secondary amine with ethylene cyanohydrin at 300 ' C. over an alumina catalyst. Popov (66)has observed in the amrnonolysis of isomeric butyl d carbon or platinum-silica gel catalyst that OH group affects the nature of the reaction. reases in the order primary, secondary, and tertiary butyl alcohol. Activated carbon and platinum supported on silica gel were Eound to be the most effective of the several materials investigated as catalysts for the ammonolysis of primary
batch proce cerned with
carried out a n extensive study of the and ammonia by both continuous and One of the objectives of the study was conlling the reaction to produce primary and ter-
lsso
INDUSTRIAL AND ENGINEERPNG CHEMISTRY
Table IV. Addition of Primary and Secondary Ethanolamines to an Ammonia-Ethylene Oxide System Mole of Seoondarv Ethanolamine Oxide Added/Mole Molar Ratio of Ethylene Oxide 3:l 0.18 0.23 5:1 0.33 10:1 15:l 0.43
":/Ethylene
3:l
6:l 1O:l
Moles of Primers Ethanolamine Added/Mole. of Ethylene Oxide 0.39 0.65 1.81
Product
% Prirnary 30 40 55 66
% Tertiary 70
60 45 35
Product
% Secondary
% ' Tertiary
40
60 40 21
60 75
Giary ethanolamines with the exclusion of secondary, or secondary and tertiary, ethanolamines with the exclusion of primary. Reaction rate data were collected and rate constants a t several temperatures were determined. The rate of reaction of ethylene oxide with primary and secondary amines is greater than with ammonia, consequently a large excess of ammonia is required if primary and secondary ethanolamines are desired. The reaction of ethylene oxide and ammonia follows a second order reaction. With the addition of known amounts of primary or secondary ethanolamines to the reactants, the equilibrium is shifted to exclude further formation of the amine added, This effect, as well as the effect of ammonia-ethylene oxide molar ratio, is readily seen in Table IV. At higher temperatures, 400 O to 450 O C., over an alumina cata1yst ethylene oxide and ammonia yield pyridine bases. The following scheme is suggested (32):
3CHzCHg
+ NHB --+ CrH6N + CO f 2H10 + 3H2
LOJ
ALKYL AND A R Y L H A L I D E S OR SULFATES Cuprous chloride is well known as a catalyst for the preparation of aromatic amines by the reaction of aryl halides with ammonia, or primary or secondary amines. It is frequently the practice to neutralize the aqueous layer, resulting from the reaction mass, with sodium hydroxide to free the excess amine or ammonia from its hydrochloride and also t o recover the copper as the hydroxide. Such a recovery of the copper catalyst is obviously tedious. Hubhes (27, 28) has devised a procedure fop recovering the copper catalyst in a form suitable for re-use withaut resorting to difficult recovery procedures. The method consists of neutralizing the aqueous solution of amine hydrochloride or ammonium chloride with sodium hydroxide after first separating off an organic layer containing the aromatic amine. The neutralization is carried to a point where most of the amine or ammonia is liberated but the copper salt still remains in solution. This copper salt solution is concentrated slightly to compensate for the water formed during the neutralization. Any precipitated sodium chloride is filtered, and the copper salt in saturated brine solution is returned to the process without isole tion. Excellent yields of N-methylaniline are obtained by this procedure. A procedure for the manufacture of 1,4-dialkylamino-2-butenes has been developed by Morey (36)which is based on reacting 1,4dichloro-Sbutene a t 60" to 90" C. with such amines as dibutylamine, diisobutylamine, and diisopropylamine. Yields in the eange of 50 to 94%, based on the chloro compound, are obtained. In like manner, 3,4-dialkylamine-l-buteneswere prepared in somewhat lower yields (36). Oxley et al. (@) observe that in the reaction of an alkyl halide with aqueous ammonia, the formation of Secondary and tertiary amines can be largely eliminated by the use of ammonium halide in the reaction mixture. Monobutylamine is obtained in 81% yield by reacting butyl chloride with 2
Vol. 41, No. 9
moles of ammonia in the presence of 10 moles of ammonium chloride. Aminonitriles have been prepared (1) by reacting monochloroalkylnitriles with ammonia. The reaction is carried out a t 125 to 150 pounds per gquare inch at approximately room temperature. Ten moles of ammonia per mole of chloronitrile are used. The yields of aminonitrile in most cases are in the range of 80 to 90% based on the starting chloronitrile. Similarly, Mostek (37) reports the preparation of imidodiacetonitrile by treating chloroacetonitrile with ammonia in a somewhat lower molar ratio &ecording to the following equation:
2CI--CH&N
-t- 3NHa ----jc NH(CH2CN)z
+ 2NH4CI
I n reacting diethanolamine with dimethyl sulfate, Gresham (23)has made the interesting discovery that with the use of sodium carbonate to neutralize the acidity developing from the decomposition of the dimethyl sulfate, yields in the range of 90% of N-alkylated diethanolamines are obtained, whereas if sodium hydroxide is used, yields drop to approximately 60% and considerable alkylation of the alcoholic (-OH) group is experienced. Speck (64)has observed that monochlorobenzene is useful in separating monoethanolamine from a mixture of mono-, di-, and triethanolamines. The monochlorobenzene-monoethanolamine azeotrope, distilling at 124" C., is easily separated from diethanolamine boiling a t 268 O (5. a t 760 mm. and the triethanolamine boiling at 278 O C.at 150 mm. A related development involves an analytical procedure devised for separation of ammonia, primary, secondary, and tertiary methylamines by a chromatographic technique using potato starch as the adsorbent and butyl alcohol as the solvent, The method is reported to be well adapted to controlling purity of amines and preparation of pure samples (21). Homeyer ($6)observes that N,N'-dimethylurea may be prepared by reacting slightly less than the theoretical quantity of phosgene with methylamine in an aqueous solution. Sodium hydroxide is used if necessary to keep the reaction mass essentially neutral. The yield is 90% of theory based on the amine. An excess over the theoretical amount of phosgene results in lower yields due to side reactions. A method has been devised (7') for making a 0,r-dihydroxyalkylamine by treating a halogen derivative of a cyclic ether oxide with ammonia or a primary or secondary amine and subsequently decomposing the cyclic ether oxide to the corresponding dihydroxy amine. Nagy (38) has prepared unsymmetrical 1,5-disubstituted biguanides by reacting substituted Scyanoguanides with primary or secondary amines. H Reaction of dicyanimide NsC-N--C=N, with aromatic amines leads to 1,5-diarylbiguanides (39). Mackay and Paden (29) have shown that guanides of the type illustrated with the following formula R. C
may be converted to the corresponding diamines by replacing the hydroxyl group with a -NH2 group by treatment with ammonia a t 300' to 400" C. a t 2000 pounds per square inch pressure.
LITERATURE CITED Bauer, 0. Vi'., and Teter, J. W. (to Sinclair Refining Co.), U. S. Patent 2,443,292 (June 15, 1948). (2) Boizrow. A,. Offiae of Military Government for Germany (U. S.),
(1) .
I
FIAT Final Rept. 716 (1948).
\
September 1949
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
(3) Boyd, Mary L.,and Winkler, C. A., Can. J. Research, 25B,38796 (1947). (4) Buc, S. R.,and Ford, J. H. (to the Upjohn Co.), U. S. Patent 2,448,013(Aug. 31, 1948). (5) Burnstein, H. I., and Long, D. (to Quaker Chemical Product5 Corp.), U.8.Patent 2,441,130(May 11, 1948). (6) Caldwell, H. P., Jr., and Chapman, H. D. (to S Oil Co.), U. 8.Patent 2,450,632(Oct. 5,1948). (7) Ciba, French Patent 934,094(May 11. 1948). (8) Compagnie de Produits Chimiques et Electrometallurgiques Alais Froges et Camargue, British Patent 690,768 (July 28, 1947). (9) Danforih, J. D. (to Universal Oil Products Co.). U. S. Patent 2,449,644(Sept. 21, 1948). (10) Denton, W.I., and Bishop, R. B. (to Socony-Vacuum Oil Co.), U. S. Patent 2,460,636-(0ct. 5. 1948). (11)Zbid., 2,450,637. (12)Zbid., 2,450,638. (13) Zbid., 2,450,639. (14) Zbid., 2,450,640. (15)Zbid., 2,450,641. (16)Ibid., 2,450,642. (17) Dewing, T., British Intelligence Objectives Sub-Committee, London, Rept. 766, Nos. 22 and 24,p. 17. (18) Dixon, J. K.,and Cook, E. W. (to American Cyanamid Co.), U.8. Patent 2,439,359(April 6,1948). (19) Erickson, J. G. (to American Cyanamid Co.), U. 8. Patent 2,451,436(Oct. 12,1948). (20) Ferrero, P., Berbe, F., and Flamme, L. R., Bull. 900. Ch'hins. Belgee, 56,349-68 (1947). (21) Fuks, N. A., and Rappoport, M. A., Dolelady Akad. Naule. S.S.S.R., 60,1219-21 (1948). (22) Gresham, W . F. (to E. I. du Pont de Nemours & Co.), U.8.Patent 2,443,420(June 15, 1948). (23) Zbb?., 2,451,942(Oct. 19,1948). (24) Zbid., 2,452,187(Oct. 26, 1948). , 325 (25) Hanmer, R. S., and Swann, S., Jr., IND.ENG.C ~ M .41, f,1949). ---, (26) Homewr, A. H.(to Mallinckrodt Chemical Works), U. S. Patent 2,444,023(June 29,1948). (27) Hughes, E. C. (to Standard Oil Co.), U. 8. Patent 2,445,932 (Deo. 14, 1948). (28) Zbid., 2,455,931. (29) Mackay, J. S.,and Paden, J. H. (to American Cyanamid Co.), U. S.Patent 2,459,710(Jan. 18,1949). (30) McLamore, W. M. (to Shell Development Co.), U. 9. Patent 2,451,852(Oct. 19,1948). (31) Mahan, J. E.(to shillips Petroleum Co.), U. 8.Patent 2,432,532 (Dec. 16, 1947).
1851
(82) Mdinovski& M. S., and Moryganov. B. N.. J. AnnlJPd Ph-. (U.B.s.R.), 20,630 (1947). (33) Marisic, M.M., Denton, W. I., and Bishop, R. B. (to SoconyVacuum oil Go.), U.S.Patent 2,450,677(Oot. 5,1948). (34)Zbid., 2,450,678. (35) Morey, G . H. (to Commercial Solvents Corp.), U. 9. Patent 2,440,724(May 4, 1948). (36) Zbid., 2,441,669(May 18,1948). (37) Mbstek, J. L. (to Sinclair Refining Co.), U. S. Patent 2,442,S47 (June 1,1948). (38) Nam, D. E. (to American Cyanamid Co.), U. 5. Patent 2,455.896 (Dec. 7,1948). (39) Zbid,, 2,455,897. (40) Nomin6, G.J. J., French Patent 935,202(June 14,1948). (41) Oxley, H. F., Thomas, E. B., Nichols, F. S., British Patent 611,593 (Nov. 1, 1948). (42) Phillips Petroleum Co., British Patent 609,059 (Sept. 24, 1948). (43) Ibid., 610,987(Oct. 22, 1948). (44) Popov, M. A., J. Gen. Chem. (U.X.X.R.), 18,438-42(1948). (46) Zbid., pp. 1109-12. (46) Potts, R. H.(to Armour & Co.), U.8.Patent 2,448,275(Aug. 31, (1948). (47) Prichard, W.W. (to E. I. du Pont de Nemours & Co.), U. 8.Patent 2,456,316(Des. 14, 1948). (48) Reutenauer and Lacombe, Bull. mens. ZTERB. No. 9, 30-1 (1947). (49)Zbid., Oldi&neum, 2, 500-3 (1947). (50) Richmond, H.H.,Meyers, G. S., and Wright, G. F., J. Am. Chern. Xoc., 70, 3659-64 (1948). (51) Robinson, C. N., and Olin, J. F. (to Sharples Chemicals, Inc.), U. 8. Patent 2,452,602(Nov. 2, 1948). (52) Rose, J. D., British Intelligence Objectives Sub-committee, London, Final Rept. 359,item 22. (53) Smith, E. F. (to Commercial Solvents Corp.), U. S. Patent 2,456,699(Dec. 14,1948). (54) Speck, J. C. (to United States of America), U. S. Patent 2,449,152 (SeDt. 14, 1948). (55) Stegemeyei, L. A. (to Emery Industries, Inc.), U. S. Patent 2,460,772(Fbb. 1, 1949). (56) S ridley, T. W. (to United States of America), 45,892(July 27,1948). (57) Teter, J. W., and Stookey, R. H. (to Sinclair Refining Co.), U. S Patent 2,461,010(Feb. 8, 1949). (58) Weston, A.W. (to Abbott Laboratories), U. 5. Patent 2,437,984 (March 16,1948). RFICBIVFID M a y 5, 1949. Contribution 80 from Jackson Laboratory, E. 1. du Pont de Nemours & Company, Inc.
COMBUSTION BERNARD LEWIS and GUENTHER von ELBE CENTRAL EXPERIMENT STATION,
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U. 5.
BUREAU OF MINES, PITTSBURGH, P A .
URING 1948 numerous papers on gaseous combustion have appeared. I n the field of fundamental research, interest of the investigators is concentrated on the theory of flame propagation, stability and structure of flames, spark ignition, and chemistry and mechanism of oxidation reactions. In applied research some diminution of interest in aircraft engines of the piston type is discernible, and the gas turbine promises t o compete with piston engines also in other fields oE application. It may be surmised that many investigations on engines, particularly of the jet type, are still restricted by security classification and that the actual volume of literature is considerably larger than shown here. This ais0 applies t o propehnts of all types, and high explosives. On the latter subject, interest in the effect of shaped or hollow charges is noticeable. Combuation in furnaces is an active field of research, and many papers deal with the related subject of smoke abatement. Several contribustions are noted on the subject of hazard contr This survey is eoncerned mainly appeared in the open literature during the latter part of 1947
and most of 1948. In view of the large number of papers, it is not possible t o vouch for completeness of coverage. It is hoped that papers that are not included in this review will come to the reviewers' attention forjnclusion in the next report.
NTAL INVESTIGAT10NS SEOUS COMBUSTION Theoretical investigations on flame propagation have been confined to one-dimensional propagation of plane combustion waves in nonturbulent explosive gases. Basic equations relating heat conduction, diffusion, and chemical processes have been formulated by Zeldovich (891) and used for a limited investigation of the steady-state combustion wave. Tanford and Pease (2667) have further elaborated on their concept of diffusion of active particles (chiefly hydrogen atoms) as the controlling factor of combustion-wave propagation and have derived several qusntitative relations that agree well with experimental facts. On the other hand, Hoare and Linnett (123) have pointed out that the derived relationships, such as the variation of burning velocity
