Checked by A. DeMeijere and K. B. Wiberg.
1. Procedure
A.
N,N,N-Trimethylcyclooctylammonium iodide. To a
2-l., three-necked, round-bottomed flask equipped with a
stirrer,
condenser,
drying tube, and pressure-equalizing dropping funnel are added
155.3 g. (1 mole) of N,N-dimethylcyclooctylamine (Note
1) and
700 ml. of reagent grade methanol. To the stirred solution is added
170.3 g. (1.2 moles) of iodomethane (Note
2) dropwise over a 30-minute period. The flask is cooled intermittently with an
ice bath to keep the reaction temperature at approximately 25° (Note
3). After 1 hour the bath is removed and the reaction mixture is allowed to stir at 25° for an additional 3 hours.
The light yellow solution is transferred to a 2-l. round-bottomed flask, and the solvent is removed under reduced pressure (Note
4) with slight warming. The solid product is triturated with
500 ml. of diethyl ether, filtered, and washed with three
200-ml. portions of diethyl ether. The white solid (
291–296 g.) is dried under reduced pressure, m.p.
269–270° dec. (Note
5).
C.
trans-Cyclooctene. A
500-ml., three-necked, round-bottomed flask is equipped with a
nitrogen inlet capillary tube (Note
9), a
short (10–20 cm.) unpacked column (Note
10), and a pressure-equalizing dropping funnel. The round-bottomed flask is connected by the unpacked column to a
100-ml. trap cooled in an ice bath. This trap is then connected to a
200-ml. trap cooled in dry ice-acetone (Note
11). The flask is heated in an
oil bath to 110–125°, and the apparatus is evacuated to a pressure of
ca. 10 mm. under a constant sweep of
nitrogen. The hydroxide solution is added dropwise at approximately the rate of decomposition of the quaternary
ammonium hydroxide (Note
12).
The combined distillates from the cold traps are allowed to come to room temperature (Note
13) and are placed in a
1-l. separatory funnel with
200 ml. of 5% hydrochloric acid solution. The mixture of
cis- and
trans-cyclooctenes (Note
14) is extracted with
200 ml. of n-pentane and subsequently with two
50-ml. portions of n-pentane. The
n-pentane extracts are combined and washed with
170 ml. of 5% sodium bicarbonate solution.
To a 1-l. separatory funnel is added
ca. 500 ml. of 20% aqueous silver nitrate solution (100 g. of Mallinckrodt C.P. crystals to ca. 500 ml. of water). The
pentane solution is added to the separatory funnel in five approximately equal portions, with intermittent shaking until all the
silver nitrate complex has gone into solution (Note
15).
The product is distilled under reduced pressure through a
short (8 cm.) Vigreux column (Note
17) and has b.p.
75° (78 mm.),
44° (23 mm.),
n25D = 1.4741,
d425 = 0.8456. The yield of pure
trans-cyclooctene is
15.0 – 15.3 g. (
40%) (Note
18), (Note
19), (Note
20), (Note
21).
2. Notes
4. It is convenient to use a rotary evaporator for removal of the solvents.
5. After one recrystallization from an
acetone-methanol mixture, the compound melts at
273–275° dec. The compound is sufficiently pure for the next step in the synthesis without recrystallization.
6.
Mallinckrodt purified silver oxide powder was used. The reaction flask should be protected from direct sunlight with a suitable wrapping.
7. The flask may be rinsed with a minimum of water and transferred to the dropping funnel. The total volume of hydroxide solution at this point should not exceed 100 ml.
8. The conversion of the quaternary ammonium iodide to the hydroxide may also be carried out using a strongly basic ion exchange resin.
4
9. The decomposition should be carried out under a constant sweep of
nitrogen. The
nitrogen may be introduced through the pressure-equalizing dropping funnel if that is more convenient.
10. The unpacked column should be wrapped with a heating tape, or Nichrome heating wire, and kept at
ca. 110° throughout the decomposition.
11. The reaction is stopped and the trap, cooled in dry ice-acetone, is emptied when the reaction is
ca. one half finished to prevent plugging by ice. Most of the olefinic products are found in the first trap. The second trap contains mostly
trimethylamine and water.
12. About 3 hours is required to add the hydroxide solution. The rate of addition may be increased, but considerable foaming occurs during the decomposition, and caution should be taken that the hydroxide does not foam over into the traps.
13. This part of the experiment should be carried out in a
hood because
trimethylamine is evolved.
15. If the
pentane solution is added to the
silver nitrate solution too rapidly, the
trans-cyclooctene forms a dark precipitate that is difficult to get into solution. This situation can, however, be remedied by the addition of more
silver nitrate solution and continued shaking.
16. The
pentane is removed and
ca. 11 g. of
cis-cyclooctene is obtained on distillation, b.p.
65° (59 mm.);
n25D = 1.4684.
17. Considerable foaming occurs during distillation of
trans-cyclooctene. The distillation may therefore be facilitated by use of a
distilling adapter with a foam trap. The distilling adapter (5225) may be purchased from Ace Glass Incorporated, Vineland, New Jersey. The bath temperature should be kept below 100° owing to the possibility of isomerization to
cis-olefin and polymerization.
6 The distillation should be carried out as rapidly as possible because the condensed product evaporates under prolonged exposure to reduced pressure.
18. The submitters carried out this preparation on a 1.0-mole scale and obtained
49–51 g. (
45–46%) of
trans-cyclooctene.
20.
trans-Cyclooctene is stable for at least 1 year if kept under refrigeration and if a free radical inhibitor is used (
e.g. di-t-butyl-resorcinol). The compound has a very disagreeable odor.
3. Discussion
This procedure illustrates a general method for preparing olefins by the elimination of an amine and a β-hydrogen atom.
11 The present method is more convenient for adaptation to large-scale laboratory preparation than is the Wittig modification, which utilizes liquid
ammonia; both methods give essentially the same overall yield of
trans-cyclooctene.
The preparation of olefins
via their thiocarbonate
10 is a stereo-specific elimination reaction which may be used to advantage when a mixture of
cis- and
trans-olefins is difficult to separate. However, all the reagents required to prepare the thiocarbonate are not readily available.
Appendix
Compounds Referenced (Chemical Abstracts Registry Number)
hydrochloric acid (7647-01-0)
ammonia (7664-41-7)
methanol (67-56-1)
diethyl ether (60-29-7)
sodium bicarbonate (144-55-8)
silver oxide,
silver oxide powder (20667-12-3)
silver nitrate (7761-88-8)
nitrogen (7727-37-9)
ammonium hydroxide (1336-21-6)
iodomethane (74-88-4)
Pentane,
n-PENTANE (109-66-0)
Trimethylamine (75-50-3)
Phenyllithium (591-51-5)
magnesium sulfate (7487-88-9)
acetone-methanol (590-90-9)
potassium amide
β-PHENYLETHYLDIMETHYLAMINE (1126-71-2)
Methyllithium (917-54-4)
dimethyl sulfoxide (67-68-5)
N,N-dimethylcyclooctylamine
N,N,N-trimethylcyclooctylammonium iodide,
trimethylcyclooctylammonium iodide
N,N,N-trimethylcyclooctylammonium hydroxide
Cyclooctylamine (5452-37-9)
3-nitro-3-methylpimelonitrile
N,N,N-trimethylcyclooctylammonium bromide
triisooctyl phosphite
potassium t-butoxide (865-47-4)
cis-cyclooctene (931-87-3)
trans-Cyclooctene (931-89-5)
di-t-butyl-resorcinol
trans-1,2-cyclooctene thiocarbonate
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