693

Ziegler Alcohol Synthesis

(Ziegler Higher Alcohol Synthesis,
Alfol Process, Ziegler-Alfol
Process, Ziegler-Alfol Synthesis)

A. GENERAL DESCRIPTION OF THE REACTION

This reaction was first reported by Ziegler in 1955.1 It is an industrial production of

higher and linear primary alcohols with an even number of carbon atoms, involving these
sequential steps: (a) synthesis of triethylaluminum from aluminum, hydrogen, and ethylene;
(b) chain growth reaction between triethylaluminum and ethylene to form higher molecu-
lar weight trialkylaluminum; (c) oxidation of resulting trialkylaluminum to aluminum alk-
oxides (or alcoholates); and (d) the hydrolysis of aluminum alkoxides to aluminum hydrox-
ide and the desired alcohols.2 In the literature, this reaction is known as the Ziegler alcohol
synthesis,2b,3 Ziegler higher alcohol synthesis,3d,3e Ziegler higher-alcohol synthesis,2b or
simply Ziegler synthesis.3c,4 The alcohols prepared by this process are generally referred
to as the Ziegler alcohols,2a,5 and triethylaluminum is known as the Ziegler catalyst.6 In
addition, because this process was first implemented by Sonoco in 19627 to produce a series
of long chain alcohols, the reaction is also termed as the Alfol process,2a,6,8 Ziegler/Alfol
process,9 Ziegler-Alfol process,2a Ziegler ALFOL process,10 or Ziegler-Alfol synthesis.9a
The alcohols are also named as Alfol 6, 8, 1214, etc.6
This process has been used to produce alcohols of carbon atom distributions from C2 to
beyond C26 ,11 of which the molecular weight distribution follows the Poisson distribution.12
At the stage of triethylaluminum synthesis, two thirds of the prepared triethylaluminum
is recycled to the hydrogenation step to form more triethylaluminum, as shown in the

Comprehensive Organic Name Reactions and Reagents, by Zerong Wang

Copyright © 2010 John Wiley & Sons, Inc.

3134
 PROPOSED MECHANISMS 3135

reaction scheme, and only one third of triethylaluminum enters the chain growth reaction.7
During the second step, the chain growth reaction undergoes smoothly to form higher
molecular weights of trialkylaluminum at a relatively low temperature range (e.g., 60–
120◦ C), whereas at a higher temperature range (e.g., 120–150◦ C), a thermal displacement
reaction occurs, offering long chain α-olefins. When the temperature is >150◦ C, dimeriza-
tion of the α-olefins takes place.13 However, in the presence of nickel, cobalt, and platinum,
the thermal displacement reaction occurs at a relatively lower temperature (e.g., 50◦ C).14
At the oxidation stage, the reaction is carried out stepwise by carefully passing dried air
through the mixture of trialkylaluminum while cooling, owing to the different reactivities
of partially oxidized trialkylalumina.7
The by-product of this reaction (i.e., aluminum hydroxide) can be converted into alumina
via dehydration,2b,3d−2f,9 and the alumina is known as the Ziegler alumina.3d High purity
alumina (such as γ-alumina3g ) has high commercial value for the production of catalysts
and for improving the economy of the Alfol process.2a

B. GENERAL REACTION SCHEME

C. PROPOSED MECHANISMS

A simple illustration of the reaction mechanism is outlined here.

3136 ZIEGLER ALCOHOL SYNTHESIS

D. MODIFICATION

This reaction has been extensively modified. The most important modification was per-
formed by the Ethyl Corporation (now a part of BP/Amoco and operated by Condea) in
19647,10 to produce alcohols with a narrower molecular weight distribution, known as the
Epal process.2a,7 In this modification, the trialkylaluminum at the stage of the chain growth
reaction is transalkylated by a C4 -C10 olefin mixture to begin a new chain growth reaction
between ethylene and (C4 -C10 )alkylaluminum. Afterward, the new alkylaluminum is fur-
ther transalkylated with a C12 -C18 n-α-olefin mixture at 200◦ C (35 kPa). After separation
of olefins and trialkylaluminum via distillation, the trialkylaluminum is treated in a man-
ner similar to that in the Alfol process.2a,7 Although this modification can make higher
alcohols of a narrow molecular weight distribution, the alcohols also are branched.2a Fur-
thermore, Chevron has applied this reaction to produce high purity linear α-olefins following
a Schulz-Flory distribution.15 Other modifications include the application of diethylalu-
minum hydride rather than triethylaluminum for the chain growth reaction,16 and the use of
aluminum alkoxides for the oxyethylation of alcohols and esters to make polyoxyethylene
glycols.4 It should be pointed out that 2-phenylethanol has been prepared by Ziegler via the
transalkylation with styrene.1a

E. APPLICATIONS

This reaction has wide applications in industry to produce a series of long chain pri-
mary alcohols, which may be used for cosmetics,15 or further converted into nonionic15 or
anionic2a,8b detergents.

F. RELATED REACTIONS

N/A
 REFERENCES 3137

G. CITED EXPERIMENTAL EXAMPLES

Reference 17.

To a mixture of 40 mL n-hexane, 41.0 g styrene (0.394 mol), and 24.0 g 98% triisobuty-
laluminum (0.119 mol) was added 0.1 g nickel acetylacetonate. The solution was refluxed
for 30 min; during this period 8.40 L isobutene (corrected to normal temperature and pres-
sure) were evolved. The resulting mixture was diluted with 30 mL hexane and cooled to
0◦ C, then CO2 and moisture-free oxygen were bubbled into the solution at a rate of 3.5 L/h.
After 8 h the air flow was stopped and pure oxygen was bubbled through the solution for
another 8 h. The oxidation products were then hydrolyzed at 0◦ C by 300 mL 8% H2 SO4 .
The oily products were extracted by ether, and dried over Na2 SO4 . The ether and most of
the hexane were evaporated, and the residue was analyzed. Among the products, 4.07 g
acetophenone was found via the quantitative hydroxylamine hydrochloride method, which
was then removed from the reaction mixture. 1-Phenylethanol was identified by oxidizing
the residue with a stoichiometric amount of CrO3 in acetic acid and formation of the deriva-
tive of 2,4-dinitrophenylhydrazone. The resulting oxidized product, 2-phenylacetaldehyde
was removed by treatment with a saturated solution of KHSO3 . 2-Phenylethanol was iden-
tified as the p-nitrobenzoate with m.p. at 63◦ C. The total quantity of 1-phenylethanol and
2-phenylethanol, following the procedure of Petersen, was 36.0 g, and 1-phenylethanol was
∼14.9% of the mixture of phenylethanols by infrared analysis. In one instance, the product
obtained from 59.5 g styrene and 35.9 g triisobutylaluminum was divided into four parts,
each part was oxidized for a different length of time at 0.5, 1.5, 10.0, and 16.0 h, respectively,
and it was found that the oxidation yield was 38%, 58%, 70%, and 93% for correspond-
ing duration of oxidation. (Note: 0.119 mol of triisobutylaluminum after transalkylation
afforded only 0.119 mol × 3 = 0.357 mol of isobutene, which corresponds to a volume of
(0.357 × 22.4 L) = 8.0 L at 25◦ C and 1 atm.)

Other references related to the Ziegler alcohol synthesis are cited in the literature.18

H. REFERENCES

1. (a) Ziegler, K.; Krupp, F. and Zosel, K., Angew. Chem., 1955, 67, 425. (b) Ziegler, K.; Holzkamp,
E.; Breil, H. and Martin, H., Angew. Chem., 1955, 67, 426.
2. (a) Fell, B., “Raw Materials and Intermediate Products for Anionic Surfactant Synthesis,”
in Anionic Surfactants, Organic Chemistry, Surfactant Science Series, Vol. 56, ed. Stache, H. W.,
3138 ZIEGLER ALCOHOL SYNTHESIS

Marcel Dekker, New York, 1995, pp. 1–38. (b) Buss, W. C. and Kluksdahl, H. E., U. S. Pat., Mar.
15, 1977, 4,012,313.
3. (a) Weissermel, K. and Arpe, H.-J., Industrial Organic Chemistry, 4th ed., Wiley-VCH,
Weinheim, 2003, pp. 210–211. (b) Meyer, A.; Noweck, K.; Reichenauer, A. and Schimanski,
J., U. S. Pat., Sept. 3, 1991, 5,045,519. (c) Jacques, R. and Dupin, T., U. S. Pat., Apr. 30, 1985,
4,514,511. (d) O’Hara, M. J. and Johnson, R. W., U. S. Pat., Jan. 5, 1982, 4,309,277. (e) Buss,
W. C. and Kluksdahl, H. E., U. S. Pat., Dec. 9, 1980, 4,238,372. (f) Beuther, H.; Kehl, W. L. and
Swift, H. E., U. S. Pat., May 10, 1977, 4,022,839. (g) Leach, B. L., U. S. Pat., Nov. 30, 1976,
3,994,982.
4. Bialowas, E. and Szymanowski, J., Ind. Eng. Chem. Res., 2004, 43, 6267.
5. Hreczucht, W., Ind. Eng. Chem. Res., 1995, 34, 410.
6. Masaru, A.; Yoshio, O.; Akio, M. and Takehiko, I., U. S. Pat., Jan. 24, 1989, 4,800,034.
7. All about Fatty Alcohols, Saturated Fatty Alcohols, CONDEA, Hamburg 2000.
8. (a) Bulgakov, R. G.; Kuleshov, S. P.; Karamzina, D. S.; Makhmutov, A. R.; Vafin, R. R.; Shestopal,
Y. L.; Mullagaliev, I. R.; Monakov, Y. B. and Dzhemilev, U. M., Kinet. & Catal., 2006, 47, 737.
(b) Porter, M. R., “Anionic Detergents,” in Lipid Technologies and Applications, ed. Gunstone,
F. D. and Padley, F. B., Marcel Dekker, New York, 1997, p. 585. (c) Maurice, B.; Jacques, L.;
Pierre, M.; Guy, P. and Nicole, T., U. S. Pat., Aug. 23, 1988, 4,766,228.
9. (a) Klaus, N.; Jurgen, S. and Arnold, M., U. S. Pat., Feb. 29, 2000, 6,030,599. (b) Arnold, M.;
Klaus, N. and Ansgar, R., U. S. Pat., Oct. 8, 1991, 5,055,019.
10. Schmidt, F., Appl. Catal. A: General, 2001, 221, 15.
11. Lundeen, A. and Poe, R., “Alpha-Alcohols,” in Encyclopedia of Chemical Processing and Design,
ed. McKetta, J. J. and Cunningham, W. A., Marcel Dekker, New York, 1977, 2, p. 465.
12. (a) Wesslau, H., Ann., 1960, 629, 198. (b) Ziegler, K.; Gellert, H. G.; Zosel, K.; Holzkamp, E.;
Schnieder, J.; Soll, M. and Kroll, W. R., Ann., 1960, 629, 121.
13. Ziegler, K. and Gellert, H. G., U. S. Pat., Jan. 11, 1955, 2,699,457.
14. Skinner, W. A.; Bishop, E.; Cambour, P.; Fuqua, S. and Lim, P., Ind. Eng. Chem., 1960, 52, 695.
15. Edwards, C. L., “Polyoxyethylene Alcohols” in Nonionic Surfactants: Physical Chemistry, ed.
van Os, N. M. and Schick, M. J., Marcel Dekker, New York, 1998, pp. 87–122.
16. Starks, C. M.; Krehbiel, D. D.; Atwood, M. T. and Feighner, G. C., I & EC Prod. Res. Dev., 1964,
3, 19.
17. Natta, G.; Pino, P.; Mazzanti, G.; Longi, P. and Bernardini, F., J. Am. Chem. Soc., 1959, 81, 2561.
18. (a) Armor, J.; Bedel, L.; Vinek, H. and Aitani, A. M., CATTECH, 2003, 7, 106.
(b) Weerasooriya, U., J. Surfact. Deterg., 1999, 2, 373. (c) Hreczuch, W. and Szy-
manowski, J., J. Am. Oil Chem. Soc., 1996, 73, 73. (d) Lindsay, K. L., “Alpha-Olefins,”
in Encyclopedia of Chemical Processing and Design, ed., McKetta, J. J. and Cunningham,
W. A., Marcel Dekker, New York, 1977, 2, p. 482. (e) Mole, T. and Jeffery, E. A.,
Organoalumininum Compounds, Elsevier, Amsterdam, 1972. (f) Knap, J. E.; Leech, R. E.; Reid,
A. J. and Tamplin, W. S., Ind. Eng. Chem., 1957, 49, 874.