HYDROXYALKYL AND OLEFINIC SUBSTITUTED gem=DIMETHYLCYCLOBUTANES JOSEPH D . PARK, N. LEE A L L P H I N , JR., SAM KWON CHOl,’ ROBERT L . S E T T I N E , * AND GLEN W. H E D R I C K 3
Department of Chemistry, University of Colorado, Boulder, Cola.
Pinonic acid, obtainable from a-pinene by oxidation, is a convenient source for dibasic acids such as pinic, sym-homopinic, and norpinic acids. In the present work the acid function of these compounds was converted to diols by lithium aluminum hydride reduction and suitable derivatives of the diols were converted to olefins. The alcohols and corresponding olefins prepared and characterized were (listed as derivatives of 2,2-dimethylcyclobutane) 1,3-di-(2-hydroxyethyI)- and 1,3-divinyl-; 1 -(2-hydroxyethyl)-3-hydroxymethyland 1 -methylene-3-vinyl-; ,and 1,3-dihydroxymethyI- and 1,3-dimethylene-. A number of methods were studied for preparation of the olefins. Dehydrohalogenation of the chloroalkyl derivatives prepared from the hydroxyalkyls (diols) was satisfactory.
HE cis-di isomer of pinonic acid, 3-acetyl-2,2dimethylTcyclobutylacetic acid ( I ) , is readily obtained from dl-apinene by permanganate oxidation ( I , 3, 75). The keto acid is a convenient source for pinolic (11) ( 7 6 ) ,p i n k (111) ( I Z ) , symhomopinic (IV) ( 6 , 7.4, and norpinic (V) (8) acids (Figure 1). Park, Settine, and Hedrick (70) have reported the preparation of 3-vinyl-, 3-ethylidene-, and 3-oxo-2,2-dimethylcyclobutylacetic acids from 11. The present paper describes synthesis of a number of 2,2-dirnethylcyclobutane compounds substituted in the 1,3- positions by hydroxyalkyl and olefinic groups (Figures 1 through 5). Esters of 111, IV, and V were converted to their corresponding glycols by lithium aluminum hydride (LAH) reduction, giving 2,2-dimethyl-1,3-di-(2hydroxyethyl) -c yclobutane ( V I ) , 2,2-dimethyI- 1- (2-hydroxyethyl) -3-hydroxymethylcyclobutane (VI I), and 2,2-dimethyl1,3-dihydroxymethylcyclobutane( V I I I ) . The synthesis of 2,2-dimethyl-I ,3-divinylcyclobutane (IX) was of primary interrst. Accordingly, the diacetate ( X ) , the dimethyl carbonate ( X I ) , and the dimethyl xanthate ( X I I ) were prepared from the glycol (VI) for pyrolysis studies, using the method described by Depuy and King ( 4 ) as a route to this divinyl compound. This particular hydrocarbon, however, was more readily obtainable by methods other than ester pyrolysis, as shown in Figures 2 and 3. Both dehydrohalogenation of 2,2-dimethyl- 1,3-di-(2-chloroethyl)-cyclobu tane ( X I I I ) , and pyrolysis of the dioxide o f , 2,2-dimethyl-1,3-di-(2-AV,:Vdimethylaminoethy1)-cyclobutane (XVI) were satisfactory synthetic methods. Pyrolysis of the dimethyl carbonate esters ( X X I I and X X I I I ) and dehydrohalogenation of the chloro compounds ( X V I I I and X X I V , Figures 4 and j), were satisfactory preparations for 2,2-dimethyl-l-methylene-3-vinylcyclobutane ( X I X ) and 2,2-dimethyl-l,3-dimethylenecyclobutane( X X V ) . In the preparation and characterization of the above glycols and olefins, many new compounds were made and are reported herein.
Present address, Taegu College, Taegu, Korea. Present address, Department of Chemistry, University of Mississippi, University, Miss. Present address, Naval Stores Laboratory, Olustee, Fla.
Experimental
Melting and boiling points are uncorrected. Analyses were by Galbraith Laboratories, Inc., Knoxville, Tenn. T h e terpene acids used in this work had properties shown in Table I.
2,Z-Dimethyl-l,3-di-(2-hydroxyethyl)-cyclobutane (VI). To a vigorously stirred solution of 76.0 grams (2.0 mole) of LAH in 1.5 liters of anhydrous diethyl ether, 350 grams (1.36 moles) of diethyl sym-homopinate were added dropwise. After several hours, of stirring, the excess LAH was decomposed cautiously by dropwise addition of 250 mi. of water and the
VI
Xlll
Figure 2. Dehydrohalogenation route to 2,2-dimethyl cyclobutane VOL. 4
NO. 3
SEPTEMBER
IX
1,3-divinyl-
1965
149
Table 1. ,I'ame
M.P. or B.P., "C.
Formula
Terpene Acids
Seutral Equiaalent Calcd.
cis-dl-Pinonic acid ( I ) 100-101 CiOH1603 184.13 sym-Homopinic acid (IV)" 119.5-121 ClOHl604 100.1 Diethyl ester of IV 100/0.07mm.b Pinic acid (111) 99-100 C9H1404 93.05 Diethyl ester of I11 76/0.06mm.b Norpinic acid ( V ) 147-9 Diethyl ester of V 59/0,08mm.b Acid IVprobably is a mixluie of cis and trans isomers. a Prepared from cis-dl-pinonicacid.
n ko
Ref. ( 1 , 3, 75)
100.4 1 ,4479
( 6 , 74) ( 78)
1 ,4466
(9) (78)
92.3
(8)
1 ,4447
(8)
Boilingpoint.
alcoholate complex was decomposed by pouring the mixture into 500 ml. of25'3, sulfuric acid. The ether layer was separated. T h e aqueous phase was extracted with more ether and the combined extracts were washed with 5 7, sodium bicarbonate solution and then with water. After drying over anhydrous sodium sulfate, the solvent was removed under reduced pressure, and VI was distilled. T h e yield was 210 grams. Data and analyses are tabulated in Table 11.
XIV
IV
Found 184.0
2,L-Dimethyl-l-(2-hydroxyethyl)-3-hydroxymethylcyclobutane (VII) and ~,P-Dimethyl-l,3-dihydroxymethylcyclobutane (VIII). These were prepared by the same procedure (Table 11). IX
XVI
V
XVll
Figure 3. Preparation and structure of 1,3-divinyl-2,2dimethyl cyclobutane via amine oxide decomposition
xxv
XXlV
XXVl
XXVll
Figure 4. Preparation and structure of 1,3-dimethyIene2,2-dimethyl cyclobutane
XVlll
XIX CHI
xx
1"z C Y
CH,6CH2c",
XXI
Figure 5. Preparation and structure of 1 -methylene-3vinyl-2,2-dimethyl cyclobutane 150
I A E C PRODUCT RESEARCH A N D DEVELOPMENT
Typical preparations of glycol esters follow. Data for each of the esters except the xanthates are given in Table I11
Diacetate (X). T h e diacetate of V I was prepared by the dropwise addition of 45.5 grams (0.58mole) of acetyl chloride in 100 ml. of anhydrous ether to a rapidly stirred solution of 50 grams (0.29 mole) of V I and 46 grams (0.58mole) of pyridine in 300 ml. of anhydrous ether. After being washed with water, then with 5Yc sodium bicarbonate solution, and again with water. the ethereal solution was dried over anhydrous sodium sulfate and the ether removed under reduced pressure. Distillation of the residue resulted in 65 grams of oil. Dimethyl Carbonate (XI). The dimethyl carbonate ester (XI) was prepared by the dropwise addition of 43.5 grams (0.46 mole) of methylchloroformate to a rapidly stirred solution of 40.0 grams (0.23 mole) of VI and 35.9 grams (0.46 mole) of pyridine in 150 ml. of anhydrous diethyl ether. After the solution had been stirred for an hour, water was added and the ethereal layer separated. T h e organic layer was washed with water and then dried over anhydrous sodium sulfate. Subsequent removal of the ether under reduced pressure and distillation of the resulting oil yielded 55.0grams. Di-S-methyl Xanthate (XII). T o a solution of 10.0 grams (0.06 mole) of 2,2-dimethyl-l,3-di-(2-hydroxyethyl)-cyclobutane in 50 ml. of refluxing toluene was added 30.0 grams (0.13 gram atom) of sodium. This mixture was refluxed for 24 hours and cooled in an ice bath and 125 ml. of anhydrous ether was added, followed by 25 ml. of carbon disulfide. After the initial reaction, excess methyl iodide (25 ml.) was added and refluxing was resumed for 2 hours. O n cooling and filtering, the filter cake was washed with ether and the solvent removed in vacuo. The crude dixanthate (13.5grams, 777,) was used without further purification for pyrolysis. hT-Tetramethyl-sym-homopinamide (XIV). T h e procedure followed was based on the work of Caserio and Roberts (2) and Wieland et a/. (77). From 20 grams (0.1 mole) of IV, 20.2 grams of X I V (797,) were obtained (b.p. 103O, 0.1 mm.; ;'n 1.4861). ANALYSIS.calculated for C 1 4 H d 2 0 2 : C, 66.03; H, 10.30. Found: C, 65.72; H , 10.37. 2,f-Dimethyl-1,3-di-(2-N,hr-dimethylaminoethyl)-cyclobutane (XV). T h e procedures followed for amine X V and its oxide (XVI) were those of Caserio and Roberts (2). From 12.7grams (0.05mole) of X I V , 9.25 grams (85%) of amine (XV) were obtained (b.p. 91-92'/3 mm.; n? 1.4530). ASALYSIS.Calculated for CI4HaoN2: C, 74.25; H, 13.34. Found: C, 73.96; H , 13.49. Diamine Oxide (XVI). . , From 7 grams (0.03mole) of X V 7.2 grams (92%) of a yellow, hygroscopic material were ob-
-
tained which were not purified further for pyrolysis.
olefins and examinations of the saturated hydrocarbons employing the above techniques gave additional elucidation of the compositions. METHOD B. Five grams (0.019 mole) of X V I were added with stirring to 25 ml. of dimethyl sulfoxide. T h e mixture was heated to 50' and held between 50' and 70' for 18 hours. After this period, the solution was heated and the volatile materials were collected in a dry ice-acetone cooled trap. Distillation of the product yielded 1.39 grams (60%) of I X . METHOD C . T h e crude xanthate ester prepared above was placed in a flask and heated to a n approximate temperature of 200'. A product distilled (b.p. 152-53'/760 mm.) which appeared to contain sulfur impurities. Analysis showed the presence of three compounds. T h e first material was subsequently shown to be IX.
2,2-Dimethyl-1,3-di-(2-chloroethyl)-cyclobutane (XIII). T h e chloride preparations and dehydrohalogenation reactions were run in accordance with Frazer et al. (5). Thionyl chloride, 27.4 grams (0.25 mole), was added dropwise to a stirred mixture of 38 grams (0.25 mole) of glycol (VI) dissolved in 100 ml. of ether and 30 grams of pyridine cooled with a n icesalt mixture. After the thionyl chloride had been added and stirred for 5 hours, the mixture was filtered cold. M'ater was added \zith 200 ml. of additional ether. T h e ethereal layer was separated and washed with 5% sodium bicarbonate, then three times with water. T h e solution was dried over anhydrous sodium sulfate and the solvent removed under reduced pressure. Distillation of the residue gave 40.0 grams of oil.
l-(2-Chloroethyl)-3-chloromethyl-2,2-dimethylcyclobutane (XVIII) and 1,3-Dichloromethyl-2,2-dimethylcyclobutane (XXIV). These were prepared by the procedure used for X I I I . Data for the three halides are given in Table 11.
2,2-Dimethyl-l-methylene-3-vinylcyclobutane (XIX) and 2,2-Dimethyl-1,3-dimethylenecyclobutane (XXV). These
2,2-Dimethyl-1,3-divinylcyclobutane (IX). METHODA. T o a rapidly stirred solution containing 20.9 grams (0.1 mole) of XI11 in 100 ml. of absolute ethanol, a potassium hydroxide solution, prepared by dissolving 14.4 grams of potassium hydroxide in 40 ml. of absolute ethanol, was added dropwise. After the initial exothermic reaction had subsided, the reaction mixture was heated and gently refluxed for a few minutes. After cooling to room temperature, it was poured into 200 ml. of water and extracted with 50 ml. of ether. T h e extract was dried over anhydrous magnesium sulfate and the ether removed. Distillation of the resulting oil yielded 9.2 grams (67%). Data for olefinic substituted dimethylcyclobutanes are tabulated in Table IV. T h e composition of the hydrocarbons was determined by GLC, using a Craig polyester succinate column and infrared spectroscopic examinations. Preparatory scale GLC was used to obtain analytical samples. Hydrogenation of the
were prepared by the dehydrochlorination procedure used in the preparation of IX. T h e N M R spectrum for XXV contained a multiplet centered a t 7 5.17, a methylene singlet at r 7.09, and a methyl singlet at T 8.70. This indicated that only exocyclic double bonds were present and that no isomerization to a conjugated cyclobutane had taken place. N M R spectra were taken using a Varian A-60 analytical spectrometer. Pure liquid samples were used with tetramethylsilane as a n internal reference. 1,3-Diethyl-2,2-dimethylcyclobutane (XVII). A 1.36gram (0.01 mole) sample of IX in 15 ml. of glacial acetic acid was hydrogenated a t room temperature over platinum oxide. After isolation and distillation of the product through a short column, 1.19 grams of X V I I were obtained (b.p. 146', 623 mm.). T h e composition was obtained by GLC and infrared spectral analysis.
Table II. Glycols and Chloro Compounds Derived from Terpene Acids Analyses Refractive B.P., Mm. Index, Densily, Calcd. Yield, 2,2-Dirnethylcyclobutanes ( "C. Hg n y d20 Formula C H 1,3-(2-Hydroxyethyl)-( V I ) 92.8 126-27 0.3 1.4741 0.9825 C i ~ H 2 ~ 0 269.65 11.69 1-( 2-Hydroxyethyl)-3-hy11.45 105 0 . 0 5 1.4762 C ~ H ~ B O 68.38 Z droxymethyl- ( V I I ) 86.7 0.9693 11.10 92 0.05 1,4707 C~H1602 66.70 1,3-Dihydroxymethyl- ( V I I I ) 81.4 0.9476 8.61 80.0 2.0 1.4767'5" 1,3-(2-Chloroethyl)- ( S I I I ) 95-96 1.00392s0 CiOHiaC12 57.74 1-(2-Chloroethyl)-3-chloro87 3.0 1,4707 1.0561 C HleCI2 55.50 8.20 methyl- ( S V I I I ) 48.0 1,3-Dichloromethyl- ( S X I V ) 72,O 82 4.0 1,4690 1.0413 CsHi4C12 53.00 7.74 Table 111.
R=(-CHz
CH~COCH~-R-CH~OCCH~(x) 0 0
69.49
H 11.73
68.75 66.79 57.63
11.64 10.90 8.61
55.21 52.92
8.12 7.79
Analyses Calcd.
live
, 0 CH,-)
Found
Glycol Esters Rejrac-
Name
c
Found
Yield.
cC
B.P., "C.
.Mm.
Hg
Index, n';
Density, d2Q
Formula
89.4
110
0.05
1.4479
1,0831
Cl4H2104
65.70
9.44
65.90
9.30
82.8
108
0.05
1.4522
1.0626
C14H2406
58.30
8.39
58.11
8.21
84.0
98
0.05
1 4528
1.0298
C13H2206
57.00
8.10
57.16
8.16
80.0
89
0.05
1 4526
0.9902
C12H2006
55.0
7.67
55.13
7.89
C
H
H
C
I1
CH30COCH2-R-CH20COCH3 0 0 I
II
CH30CO-R-CH20COCH3
0
'I
(XI)
(XXII)
0
CHaOCO-R-OCOCH3
(XXIII)
Table IV. Yield, 2,2-Dimethylc~clobutanes
1,3-Divinyl ( I X ) 1-Methylene-3-vinyl ( X I X ) 1,3-Dirnethylene (XXV) a
% 67.0 66.0 80.0
BdP., C. 147 121 92
1,3-Substituted Olefinic 2,2-Dimethylcyclobutane~~ .tfm. Hg
Refractile Index, n '2
623 622 626
1.4473 1 ,4457 1.4441
.4nalyses Cnlcd.
Density. d1Q 0.8199 0.7911
0,7744
Formula
C
CioHio ClH14 CaH12
88.20 88.50 89.65
H 11.80 11 .50 10.35
Found
C 87.94 88.22 89.53
H 12.01 11.69 10.49
Dehydrohnlogenation melhod.
VOL. 4
NO. 3
SEPTEMBER
1965
151
Table V.
butane (XXVI) (m.p. 129-32'). The infrared spectra had peaks at 4.22, 5.31, 5.88, and 6.6 to 7.5 microns as reported by Hasek and Martin (7).
Pyrolysis of Esters c /C
Compound
T e m p . , Comer"C. sion
Diacetate X Dicarbonate XI
550 525
Dicarbonate XI
515
Dicarbonate XI
490
Dicarbonate XXII Dicarbonate XXII Dicarbonate XXIII
525 510 525
Product Composition0
X(lOO%) 67 I X (16Yc), butadiene 4methyl-l,3-pentadiene (51%) 42 I X (14%). butadiene 4methyl-l,3-pentadiene (287~) 29 I X (17C,). butadiene 4methyi-l,3-pentadiene (12%) 26 XIX (26c0) 13 XIX (13%) 32 XXV (30Yc); unknown 0
+
+
+
(2%) Analyses of products completed after separation of COn and CH1OH. Material unaccounted for &as unchanged ester a
Pyrolysis of Esters X, XI, XXII, and XXIII. A 45-X 2.5cm. borosilicate glass pyrolysis tube was mounted vertically and equipped as described ( 4 ) . Prepurified nitrogen, 60 to 80 ml. per minute, was passed through the column. The ester was added at a constant rate of 0.5 ml. per minute and the distillate collected in a trap. T h e products were separated by distillation and in some cases by preparatory scale gas chromatography. The per cent conversion was determined by GLC analyses. Data on pyrolysis of esters X, X I , X X I I , and X X I I I are given in Table V. l-Ethyl-2,2,3-trimethylcyclobutane (XXI). By the above method, 2.5 grams (0.02 mole) of XIX were hydrogenated, giving X X I (b.p. 116°j620 mm., n22 1.4234). ANALYSIS.Calculated for C9H18: 85.59; H , 14.61. Found: C , 85.73;H,14.66. 1,2,2,3-Tetramethylcyclobutane (XXVII). By the reduction method described above for the preparation of I X , 2.3 grams (0.021 mole) of X X V I I were prepared from 2.35 grams (0.026 mole) ofXXV (b.p. 83'/618 mm.; nZ,O 1.4222). ANALYSIS.Calculated for C8H16: C, 85.60; H, 14.40. Found: C, 85.93; H, 14.39. Ozonolysis of 2,2-Dimethyl-1,3-divinylcyclobutane (1x1. An ozone and oxygen mixture was slowly passed through a fritted glass bubbler into a solution of 13.6 grams (0.1 mole) in 100 ml. of methylene of 2,2-dimethyl-l,3-divinylcyclobutane dichloride a t 0 '. When the reaction was complete, the ozonide solution was added dropwise to a stirred solution of 15 grams of 30y6 hydrogen peroxide, 0.5 ml. of concentrated sulfuric acid, and 30 ml. of water. The methylene dichloride was removed under reduced pressure, and the reaction mixture The aqueous solution was concenstirred overnight at 50'. trated to one half the original volume and the colorless crystalline acid that separated was removed by filtration. Recrystallization of the acid from water, follokved by careful drying, yielded 13.9 grams (0.08mole) of norpinic acid (V) (m.p. 143-45'). The norpinic acid thus prepared was a mixture of cis and trans isomers. ASALYSIS.Seutral equivalent calculated for C 8 H 1 2 0 4 : 86.0. Found: 86.9. Ozonolysis of 2,2-Dimethyl-l-methylene-3-vinylcyclobutane (XIX). The procedure for the ozonolysis of I X was used to ozonize 12.2 grams (0.1 mole) of 2,2-dimethyl-lmethylene-3-vinylc~clobutane(XIX). The acid resulting therefrom was crystallized from water and dried, yielding 10.2 grams (0.07 mole) of 3-oxo-2,2-dimethylcyclobutanecarboxylic acid (XX) (m.p. 103-104'). A mixed melting point with material obtained from the hydrolysis of 3-methylene-2,2dimethylcyclobutanecarbonitrile ( 7 9 ) showed no depression. I h e infrared spectra had strong carbonyl absorbance at 5.8 and 5.95 microns. ASALYSIS.Calculated for CiH1003: C, 59.15; H, 7.04. Found: C, 58.83;H , 6.79. Neutral equivalent calculated: 142.0. Found: 140.1. Ozonolysis of 2,2-Dimethyl-1,3-dimethylenecyclobutane (XXV). rt'ith the procedures outlined for I X , 10.8grams (0.1 mole) of XXV were ozonized. Concentration of the solution gave a crystalline product, 2,2-dimethyl-l,3-dioxocyclo-
c,
152
l & E C P R O D U C T RESEARCH A N D D E V E L O P M E N T
Discussion
Ester pyrolysis was generally unsatisfactory for the preparation of the divinylcyclobutane compounds (IX). T h e diacetate did not pyrolyze at 550°, the xanthate gave some product, and the carbonate gave low yields. At a high pyrolysis temperature (525'), the divinyl compound from the carbonate pyrolysis was not stable and decomposed, giving a mixture (51y0)of equimolar quantities of butadiene and 4methyl-l,3-pentadienes. At 490' the amount of this mixture was greatly reduced (12%). Synthesis of IX was best accomplished by other methods (Figures 3 and 4). Proof of structure of I X was obtained by oxidation (ozonolysis) of the olefin to norpinic acid, a known material, and hydrogenation which gave a mixture of cis- and trans-1,3diethyl-2,2-dimethylcyclobutane. The isomers were separated by preparative scale GLC. Schmidt and Fisher (77) of this laboratory reported the preparation and characterization of the cis and trans isomers of the diethyl-substituted cyclobutane compounds. A comparison of the infrared spectrum of the cis and trans isomers separated by GLC with spectrum of the known compounds confirmed that compound IX was a mixture of cis and trans isomers. Reduction of the olefin mixtures followed by GLC analysis was a convenient method of establishing the cis-trans compositions of IX made by the four different methods (Table VI). The only reasonable explanation for variations in composition shown in Table VI is in the purity of the acid (IV) used as raw material. Recent work in this laboratory (73) has shown that sjm-homopinic acid as prepared ( 6 , 74) from cis-dl-pinonic acid is probably a mixture of cis and trans isomers in a ratio of about 7 to 3. Purification by crystallization changes this ratio. Melting point is no criterion of purity.
Table VI.
cis-trans
Composition of Compounds
Divinylcyclobutane Composition, % trans
Synthetic Melhod
CtS
Carbonate pyrolysis Xanthate pyrolysis Dehydrochlorination Amine oxide decomposition
67
33
80 70 92
20 30 8
2,2-Dimethyl-l -methylene-3-vinylcyclobutane was converted to 2,2-dimethyl-3-oxocyclobutylcarboxylic acid (XX) by ozonolysis. The acid was identical to material prepared from 2,2-dimethyl-3-methylenecyclobutylcarbonitrile( 7 9 ) . Reduction of the olefin gave l-ethyl-2,2,3-trimethylcyclobutane (XXI). Composition of the hydrocarbon with respect to distribution of cis and trans isomers was not determined in this case. Ozonolysis of the dimethylene compound gave 2,Zdimethyl-l,3-dioxocyclobutanewhich had an infrared spectrum identical to that of the compound reported by Hasek and Martin (7). Conclusions
The reduction by lithium aluminum hydride of esters of pinic, sym-homopinic, and norpinic acids gave gem-dimethylcyclobutane diols which by degradative methods gave the following interesting olefinic substituted gem-dimethylcyclo-
butanes: 2,2-dimethyl-l,3-divinylcyclobutane; 2,2-dimethyl1-methylene-3-vinyliyclobutane; and 2,2-dimethyl-l,3-dimethylenecyclobutane. Both series of compounds-glycols and olefins-are new and deserve further, more intensive investigation. Acknowledgment
One of the authors (N. L. Allphin, Jr.) expresses his appreciation to the Minnesota Mining and Manufacturing Co., St. Paul, Minn., for its partial financial support of this work and to the Naval Stores Laboratory, USDA, Olustee, Fla., for its gift of the starting material. We further express thanks to Melvin Hanna, Chemistry Department, University of Colorado, for his patience and help in the interpretation of the KMR spectra, and to George I. Pittman, New Orleans, La., for preparation of the drawings in Figures 1-5. literature Cited (1) Baeyer, A , , Ber. 29, 326, 2776 (1896). (2) Caserio, F. F., Roberts, J. D., J . A m . Chem. Soc. 80, 5511 119SX’i. - - -,. (3) Delepine, M., Buii. Inst. Pin 3 (20),174 (1936). (4) Depuy: C. H.. King, K. W:, Chem. Rets. 60, 431 (1960). (5) Frazer. M. 3.. Gerrard. FV., Machell, G., Shepherd. B. D., Chem. Ind. 1954, p. 931. \ -
(6) Guha, P.? Ber. 70, 736 (1936). (7) Hasek, R. H., Martin, J. C.: J . Org. Chem. 27, 3743 (1962). (8) Kerschbaum, M.. Ber. 33. 891 (1900). (9) Lewis, J. B., Hedrick, G. h., J.‘ Org.’Chem. 24, 1870 (1959). (10) Park, J. D.? Settine, R. L., Hedrick, G. I V . , Ibid., 27, 902 (19 62) . (11) Schmidt, G. A , , Fisher, G. S.,Abstracts, 127th Meeting,
American Chemical Society, Cincinnati, Ohio, April 1955, page 37N. (12) Senimler, M., Ber. 44, 3665 (1911). (13) Settine, li. L.: Hedrick, G. It’., unpublished results, 1964. (14) Srinson, J. S., Lawrence, R. V., J . Org. Chem. 19, 1047 (1954). (15) Suinmers, H. B., Jr., Hedrick, G. LV., Magne, F. C., Mayne, K. Y.. Ind. En,g. Chem. 51, 549 (1959). (16) Tiemann, F., Kerschbaum. M., Ber. 33, 2665 (1900). (17) \Vieland. T.: Schafer, FV.: Bokelmann, E., Ann. 573, 99 (1951). (18) \Vielicki, E. A , , Boone, C. J., Evans, R. D.: Lytton, M. R., Summers, H. B., Jr., Hedrick, G. FV., J . Polymer Sci. 38, 307 (1933). (19) \Villiams, J. K., Central Research Department, and Barne, A. L., Elastomer Chemicals Department, E. I. du Pont de Nernours & Co., Lt’ilmington, Del. RECEIVED for review September 30, 1964 ACCEPTED June 23, 1965 Division of Organic Chemistry (in part), 146th Meeting, ACS, Denver, Colo., January 1964. Taken from the Ph.D. thesis of N. L. Allphin, Jr. (1964), University of Colorado. LVork done at the University of Colorado.
CATALYTIC COMBUSTION OF ETHYLENE ON CuO Efeect of Catahst Preparation Methods E. P. KOUTSOUKOS AND KEN NOBE Department of Engineering, Uniuersity of California? Los Angeles, Caiif.
Catalytic combustion of ethylene a t low concentrations on CuO was studied. Five CuO catalysts were prepared b y varying the amount of potassium hydroxide used in the precipitation of cupric hydroxide from aqueous cupric nitrate solutions. An empirical rate expression of the form, r = k P B n , was used to correlate the experimental data, with a reaction order of 0.60 providing the best correlation of all the kinetic data. The experimental data indicated that the activity of CuO decreased with increasing amount o f KOH used in the preparation of the catalyst (up to 25y0 greater than the stoichiometric quantity). The BET surface area and mechanical strength of the catalyst were increased b y increasing the amount of KOH.
in connection with the UCLA air pollution catalytic combustion of hydrocarbons and carbon monoxide, it was observed that the activity of copper oxide catalysts was altered by different catalyst preparation procedures. ‘For example, Blumenthal ( Z ) , observed that substantial differences in the adsorption rate of CO and COS and in the oxidation rate of CO on pure CuO could be achieved by varying the amount of potassium hydroxide used in the preparation of the catalyst. The investigation reported in this paper is an extension of Blumenthal‘s work to the study of ethylene combustion on various C u O catalysts. These catalysts Lvere prepared as in Blumenthal‘s investigation by varying the amount of K O H added to copper nitrate solutions to precipitate C L ~ ( O H ) which was then thermally decomposed to C u O . Five different C u O catalysts were prepared by varying the amount of K O H added to the copper nitrate solution from 507’ less to 50% greater than the stoichiometric quantity ECESTLY,
R research program investigating
required for the complete reaction to C u ( 0 H ) S . Care was taken to eliminate or minimize as much as possible the other variables in the preparation procedures. T h e reproducibility of the catalyst preparation procedures was also investigated. Pure C u O was selected for the combustion studies reported here rather than the CuO-Al203 catalysts as in a previous investigation ( 7 ) in order to eliminate or minimize pore diffusion effects by producing catalysts with large mean pore radii. ‘Ihe mean pore radii of pure CuO \vas about an order of magnitude larger than the CuO-.A1203 catalysts. Experimental
Five groups of C u O catalysts were prepared, differing only in the amount of K O H used in the precipitation of C u ( O H ) * from Cu(SO3)2 solutions.
Catalyst A . Sample 1 (507‘ less than stoichiometric). Four hundred and eighty-four grams of analytical reagent VOL. 4
NO. 3
SEPTEMBER 1965
153
