Sept., 1940
UNSATURATED HYDROFORRIYLATION WITH COBALT CARBONYL
ride was refluxed (about five hours) uiitil no further loss of weight was observed. The mixture was filtered and fractionally distilled through a 30-cm. Vigreux column. The yield of monochloride, b. p. 88-89" (74 mm.), was 23 g. (?O% based on sulfuryl chloride). The weight of dichloride, b. p . 122-123" (75 mm.), was 4 g. Anal. Calcd. for CTHloC12 (dichloride) : C, 50.93; H, 6.10. Found: C, 61.47; H, 6.27. The monochloride (20 8 . ) was refluxed for five hours \+ith a mixture of 50 ml. of water, 50 ml. of acetone and 50 g. of sodium carbonate. The recovered chloride amounted to 5 g., b. p. 79" (46 mm.). Rate Determinations.-[Veighed samples (0.5-1 g.) of the chlorides were made up to 50.0 ml. with aqueous alcohol (goyo alcohol and 20y0 water by volume) a t room temperature. Five-milliliter samples were sealed in soft gla2s test-tubes and heated in a thermostat a t 85.0 * 0.1 The reaction rate was followed by titration of the liberated acid with standard alkali.
possibly account for the difference in reactivity between I and 11. However, i t is noteworthy that if I is a mixture of exo- and endo-forms, these must have very similar solvolytic rate constants since the solvolysis of I follows the first-order rate law to well over SOgi., reaction as shown by Fig. 1. Further experiments are in progress on the determination of the mechanisms of displacetnent reactions of norbornyl derivatives. Acknowledgment.-We are indebted to Dr. R. C. Lord, Jr., and Mr. R . 8. McDonald for the infrared determinations. Experimental Chlorination of Bicyclo[Z,Z,l]heptane.-A
.
mixture of
48 g. of bicycl0[2,2,l]heptane,~~ 34 g. of sulfuryl chloride, 0.25 g. of benzoyl peroxide and 40 ml. of methylene chlopentachloride.
T h e properties b. p. 66-67O (2.5 mm.), m. p.
305 1
- 5 O
of t h e chloride prepared by Komppa and Beckman are very similar to those obtained in t h e present work.
(11) T h e hicyclo[2,2,l]heptane was prepared by low-pressure hydrogenation in acetic acid over platinum oxide of bicyclo[2,2,1]?63, heptene made by the method of Joshel and Rutz, THISJOURNAL, 3330 (1941), a s modified by Thomas, I n d . Eng. C k e m . , 36,310 (1944). T h e low pressure hydrogenation process is somewhat more convenie n t than t h a t descrihed by Thomas and gives n o methylcyclohexane.
Summary The peroxide-catalyzed chlorination of bicyclo[2,2,l]heptane with sulfuryl chloride was found to give norbornyl chloride as the principal monochlorination product. Norbornyl chloride solvolyzes in 230% ethanol a t 85' nine times faster than cyclopentyl chloride. CAMBRIDGE 39, MASSACHUSETTS RECEIVED OCTOBER30, 1948
__
[A COMMUNICATIOK FROM
THE
LABORATORY OF ORGASICCHEMISTRY OF
THE
U ~ I V E R S I TOFY \VISCOSSIS]
Hydroformylation of Unsaturated Compounds with a Cobalt Carbonyl Catalyst BY HOMER A
A .WD GEORGE ~ ~ KRSEK' ~
Dicobalt octacarbonyl, Coz(C0)~,proved to be quite effective and useful2in catalyzing the formation of aldehydes through the addition of carbon monoxide and hydrogen (H2CO) to alkene linkages. The present paper is concerned with improvements in the method and a survey of the usefulness and of the limitations of the hydroformylation reaction. The use of a soluble cobalt catalyst was developed from the earlier work3-6 with a Fischer-Tropsch type of insoluble catalyst. Two publications on the use of the insoluble catalyst have appeared r e ~ e n t l y . ~ ~ * The hydroformylation reaction has given good results with unsaturated compounds of quite diverse structures. Hydrocarbons of the types IiCH=CH2 and RCH=CHK, allyl ethers, a,& unsaturated esters such as acrylates, crotonates a n d fumarates, and allyl and vinyl acetates and ( 1 ) Socony-Vacuum Oil C o . Fellow, July, I947-November, 1'348. ( 2 ) Adkins and Krsek, THISJOURNAL, 70, 383 (1948). (3) Smith, H a w k a n d Golden, ibid., 52, 3221 (1930). (4) Mittasch. Winkler and Urban, German Patent 539,900, C. A , , 26, 2197 (1932). ( 5 ) Otto Roelen, U. S. Patent 2,327,066 (1943). (6) F I A T Final Report 1000. T h e Oxo Process. Issued by the O 5 c e of Military Government for Germany, through t h e Office of Technical Services of t h e U.S. Department of Commerce, PB81383. (7) Keulemans, Kwantes a n d Van Bavel, Rec. trap. chim., 67,
299 (1948). (8) Gresham, Brooks and Bruner, U. S. Patent 2,437,600 (1948).
~
~
allylidene diacetate added the elements of furmaldehyde in good to fair yields. X summary of the numerical results is given in Table I. The yields of aldehydes reported in the tables are based upon distillation of the reaction mixtures, titration with hydroxylamine hydrochloride, determination of refractive indices, and the chromatographic separation of 2,&-dinitrophenylhydrazones, as described in the experimental part of this paper. Since it is difficult to isolate an aldehyde without considerable loss, the yields in Table I should be interpreted in consideration of the more detailed results given in the experimental part for representative syntheses. The reactions were run a t 120-12.jo in benzene, under a pressure of 100-150 atrn. of hydrogen and 100-130 atm. of carbon monoxide, as measured a t 23'. These conditions differ from those used earlier with dicobalt octacarbonyl, in that benzene rather than ether was the reaction medium, the total pressure was lower, and the ratio of carbon monoxide to hydrogen was 1: 1 instead of 2 : 1. Benzene was chosen as the reaction medium after a comparison of several liquids. The hydroformylation of methyl undecylenate went twice as rapidly in benzene or methylcyclohexane as in diethyl ether and three times as rapidly as in methyl formate. The reaction went as rapidly
3052
HOMERADKINSAND GEORGEKRSEK
Vol. '71
in acetone as in benzene, but the yield of aldehyde ethers underwent simultaneous addition of -CHO isolated was lower, presumably due t o condensa- a t both the terminal and the secondary carbon tion. The hydroformylation reaction proceeds atom. well in a mixture of benzene and ethanol but the Certain a,@-unsaturated carbonyl compounds acetal of the aldehyde may be the chief product, were reduced without hydroformylation, through as described later in the hydroformylation of the action of hydrogen in the presence of cobzlt ethyl acrylate. carbonyls. Crotonaldehyde and acrolein were The catalyst for hydroformylation is apparently reduced to butyraldehyde and propionaldehyde, not poisoned by sulfur compounds, as would be respectively, while methyl vinyl ketone and true of a catalytic metal such as cobalt. The mesityl oxide gave methyl ethyl ketone and reaction of carbon monoxide and hydrogen went methyl isobutyl ketone. Similarly ethyl cinalmost as rapidly and gave approximately the namate and ethyl P- (2-furan)-acrylate gave ethyl same yield of aldehyde when diphenyl sulfide was 0-phenylpropionate and ethyl 0-(2-furan)-propipresent as when i t was not. onate. The yields with the aldehydes were 40The rate of reaction and temperatures required 50% while with the ketones and esters they were for hydroformylation, as shown by the data in in the range 70-90%. Higher yields could no Table I, are quite dependent upon the amount doubt be obtained if the optimum conditions for and ratio of catalyst to unsaturated compound. the hydrogenation and isolation of the products However, the yield of aldehyde isolated was were sought. The hydrogenation of the a,Pusually about the same in a rapid reaction as in a unsaturated carboxy compounds was apparently catalyzed by a compound soluble in benzene slow one. I n several cases the compounds are unsymmet- whose activity was not adversely affected by rically substituted derivatives of ethylene so that, the addition of diphenyl sulfide (1.2 g.) to the depending on the direction of addition, there was a cobalt carbonyl (1.6 g.). Acrolein diethyl acetal, a-vinylfuran and acrylopossibility of two isomeric aldehydes being pronitrile absorbed 50-7570 of the amount of hyduced. In four compounds of the type RCH= CH2 where R was -CO2C2H5, -CH202CCH3 and drogen and carbon monoxide required for com-CH(OZCCH&, addition of -CHO went exclu- plete hydroformylation. Apparently the desired sively to the terminal carbon, with the production reaction took place, but no aldehyde could be of aldehydes of the type RCH2CH2CH0. In the isolated from the reaction mixtures, although case of two alkenes (C2H&C=CH2 and CzHbC- qualitative tests showed them to be present. (CHa)=CHz addition of -CHO was also exclu- I t appeared that the aldehyde first formed undersively to the terminal carbon. In ethyl crotonate went further reaction. 1,%-Dihydronaphthalene, the addition of -CHO was apparently exclusively 2- (4-methylphenyl) -propene- 1,1l-bromododeceneto the carbon carrying the methyl group rather 1, 5-bromo-pentene-1 and allyl chloride absorbed about 50% as much gas as required for complete than to the one adjacent t o a carbethoxy group. In contrast with these results four alkenes of the hydroformylation but aldehydes were not found type RCH=CH2, where K was phenyl, or a- in the reaction mixture. In the case of the comnaphthyl, or ethoxymethyl, or n-butoxy, showed pounds containing a halogen, all of the cobalt addition of -CHO on the substituted carbon present in the reaction mixture was converted to atom. The aldehydes isolated in good yields a cobalt halide. l-Phenyl-butadiene-l,3, phenylwere of the structure KCH(CH3)CHO. It is acetylene, AS-octalin, phenanthrene, furan and probable that the isomeric aldehydes, KCH2CH2- acetonylacetone did not react a t an appreciable CHO, were also produced, but with one exception rate when exposed to carbon monoxide and hythey were not isolated. The absorption of hy- drogen a t 125' with dicobalt octacarbonyl in drogen and carbon monoxide in the hydroformyla- benzene. Experimental Part tion indicated a much higher yield of aldehyde Attention is again called to the precautions necessary than the 29-31% actually isolated in the four cases in handling carbon monoxide and metal carbonyls. The just mentioned. methods described in the preceding paper2 were in general Derivatives of ethylene of the type RCH=CHz, followed escept that dicohalt carbonyl was prepared in where R was n-C4HS-,n-C16HJ3-,--(CHZ)~COZCH~,benzene rather than in ether. Some of the unsaturated -cH2OC6H5, --CHzOCzH5 and -02CCH3, all compounds were obtained from commercial sources, i. e., vinyl ether, T Z * ~ D1.3991, and allylidene didcetate, gave mixtures of aldehydes of the types RCH2CHz- butyl T Z ~ 1.4172, ~ D from Carbide and Carbon Chemicals CorCHO and RCH(CH3)CHO. The alkene CzH5- poration; allyl alcohol and acrolein from Shell Chemical CH=CHCH3 also gave a mixture of CZHsCHz- Company; vinyl acetate, X * ~ D 1.3034, from the Siacet ~ from the CH(CH3)CHO and (CzH&CHCHO. It is possi- Company; and ethyl acrylate, n Z 6 1.4037, Rohm and Haas Company. Several compounds were ble that the starting materials in the case of the made by dehydration of alcohols over various catalysts : hydrocarbons and methyl undecylenate were not cyclopentanol over sulfuric acid t o cyclopentene f f Z 6 ~ homogeneous with respect to the position of the 1.4183; 2-(l-naphthyl) -ethanol over potassium hydroxdouble bond, or that migration of the double bond ide at 165" (16 mm.) t o ~ - v i n y l n a p h t h a l e n e , g ~ *15.DN 2 0 ; took place during reaction.' However, there can and p-decalol over zinc chloride at 180" to a mixture of be no doubt that vinyl acetate and the allyl (9) Cohen and Warren, J. Chem Sac., 1318 (1937).
UNSATURATED HYDROFORMYLATION WITH COBALT CARBONYL
Sept., 1949
3053
TABLE I HYDROFORMYLATION OF CARBON TO CARRON DOUBLEROXDS Compounds
'ripe, mm.
Comp. cat.,
P./&
Allyl acetate Ailyl acetate Allyl acetate Butyl vinyl ether Cyclopentene E t h y l crotonate Diethyl fumarate 2-Ethyl-butene-1 Styrene Allyl alcohol a-Vinylnaphthalene 2-Methyl-butene-1
32 80 300 105 100 80 12 120 53 60 100 140
60 60 60
1.8 1.2 0.3
23
0 . (i O.fi
Ethylene Ethylene' Allylidene diacetate Allylidene diacetate E t h y l acrylate Ethyl acrylate Ethyl acrylated
25 30 10 90 16 150 30
65 65
7.8 21.0 2.7 0.5 1.2 0.3 1.3
Vinyl acetate
15
43
4.2
Hexene-l
15
20
2.4
33 23 15 120 50 40
23
62 26 ,XI
2.2 1.6 2.1 2.4 0.0
1.5
0.6
23 50 35 42 26 29 31 25
0.6 1.6 2.0 3.6 2.2 0.6 0.6
B. p.
70yield of aldehyde
"C.
75 y-Acetoxybutyraldehyde 70 y-Acetoxyhutyraldehyde 55 y-Acetoxybutyraldehyde 31 a-Butoxypropionaldehyde 65 Cyclopentanealdehydeifl 71 Ethyl @-formylbutyrate 51 Diethyl a-formylsuccinate18 55 (3-Ethylvaleraldehyde 30 Hydratropaldehyde'@ 18 y-Hydroxyhutyraldehyde'o 29 a-(lNaphthyl)-propionaldehyde?l 53 (3-h'lethylvaleraldehyde**
55 133-136 58-59 104-105 50-51 76-77 98-99 142-143 36-36
Mm.
M., P., C.
26 746 0 01 0 04 20 0 08 35 3 28
206-207a 12fi-127a
740
323 124'1
78-79' 123-124a 67-68' 100-101b 139-140" 1.53- 134"
nZ6D
1.4150 1.4406 1 ,423fi 1.4486 1.2136 1.5148 1.4284 1.608fi
03.-
