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DOI:10.15227/orgsyn.065.0090

Organic Syntheses, Coll. Vol. 8, p.212 (1993); Vol. 65, p.90 (1987).

A GENERAL SYNTHETIC METHOD FOR THE PREPARATION

OF CONJUGATED DIENES FROM OLEFINS USING
BROMOMETHANESULFONYL BROMIDE: 1,2-
DIMETHYLENECYCLOHEXANE
[Cyclohexane, 1,2-bis(methylene)-]

Submitted by Eric Block and Mohammad Aslam1.

Checked by Jeffrey C. Weber and Leo A. Paquette.

1. Procedure
A. Bromomethanesulfonyl bromide. A 3-L, three-necked, round-bottomed flask equipped with a
mechanical stirrer, a pressure-equalized dropping funnel, and a thermometer is charged with 100 g (0.73
mol) of sym-trithiane (Note 1) suspended in 600 mL of water. Bromine (1136 g, 7.1 mol) is added with
stirring while keeping the flask temperature around 40°C (Note 2). After the addition of half of the
bromine, 600 mL of water is added and bromine addition is continued. After all of the bromine has been
added, the reaction mixture is stirred for 0.25 hr. The mixture is transferred to a 4-L separatory funnel,
the lower organic layer is separated, and the aqueous layer is extracted with two 200-mL portions of
methylene chloride (Note 3). The organic extracts are combined, washed with one 100-mL portion of
cold 5% sodium bisulfite solution and with 100 mL of water, dried over anhydrous magnesium sulfate,
and concentrated at room temperature with a rotary evaporator to a light-yellow oil. Distillation using a
short Vigreux column affords 218–249 g (42–48%) of bromomethanesulfonyl bromide as a light-yellow
oil, bp 68–69°C (0.55 mm) (Note 4) and (Note 5).
B. 1-Bromo-1-methyl-2-(bromomethylsulfonyl)cyclohexane. Four Pyrex test tubes (2.5 × 20 cm) are
charged with 1-methylcyclohexene (5.0 g per test tube; total weight 20.0 g, 0.21 mol) (Note 6).
Methylene chloride (12 mL) is added to each test tube, which is cooled in ice. An ice-cold solution of
bromomethanesulfonyl bromide (13.6 g of bromomethanesulfonyl bromide per test tube; total weight
54.4 g, 0.23 mol) in methylene chloride (12 mL) is added to each test tube with mixing at 0°C (Note 7).
The test tubes are attached with the help of several rubber bands to a Pyrex immersion well equipped
with a 45-W mercury lamp (Note 8). The immersion well is cooled by circulation of ice water (Note 9)
and immersed in a cooling bath maintained at −15°C. The reaction mixture is irradiated for 2 hr. Solid
potassium carbonate (1.5 g) is added to each test tube and the contents of the test tubes are filtered
through a small column with a glass wool plug into a 250-mL round-bottomed flask. Methylene
 chloride is removed, first on a rotary evaporator and then with a vacuum pump (1 mm), to give an
oil that gradually solidifies (68.3 g, 98%). Recrystallization from 95% ethanol (100 mL) gives white
crystals (54.3 g, 78%) (Note 10), mp 59–61°C (Note 11).
C. 1,2-Dimethylenecyclohexane. An oven-dried, 1-L, three-necked, round-bottomed flask equipped
with a mechanical stirrer, a pressure-equalized dropping funnel, and a stopper is charged with potassium
tert-butoxide (59.5 g, 0.53 mol) (Note 12) dissolved in tert-butyl alcohol–tetrahydrofuran (9:1, 400 mL
total) (Note 13) and cooled in ice. A solution of 1-bromo-1-methyl-2-(bromomethylsulfonyl)
cyclohexane (54.0 g, 0.16 mol) in tert-butyl alcohol–tetrahydrofuran (9:1, 100 mL) (Note 14) is added
dropwise over a 1-hr period. After the addition is complete the reaction mixture is stirred at room
temperature for 0.5 hr and then poured into a 2-L separatory funnel containing 500 mL of water. This
solution is extracted with two 150-mL portions of pentane. The combined pentane extracts are washed 8
times with water (500 mL) (Note 15), dried over anhydrous magnesium sulfate, and filtered. The
pentane is removed by distillation at atmospheric pressure using an efficient Vigreux column and the
residue is distilled under reduced pressure to give 11.4 g (65%) of 1,2-dimethylenecyclohexane as a
colorless liquid, bp 69–70° (90 mm) (lit.2 60–61°C, 90 mm) (Note 16) and (Note 17).

2. Notes
1. sym-Trithiane is prepared as described by Bost and Constable3 and is used without purification. It can
be purchased from Aldrich Chemical Company, Inc.
2. This is an exothermic reaction; no outside heating is required. If the temperature goes above 40°C,
the flask is cooled by ice–water.
3. In the first of these extractions, the upper phase is the organic one. In the second extraction, the
organic layer is at the bottom.
4. The product has refractive index nD20 1.5706 and spectral properties as follows: IR (neat) cm−1: 3040
(vs), 2960 (vs), 1362 (vs), 1205 (s), 1160 (vs), 1105 (m), 830 (s), 680 (s); 1H NMR (CDCl3, 60 MHz) δ:
5.05 (s).
5. The product can be synthesized on a much smaller scale with no loss in yield simply by reducing the
quantities as desired.
6. 1-Methylcyclohexene was obtained from the Aldrich Chemical Company, Inc. and was distilled
before use.
7. On occasion bromomethanesulfonyl bromide undergoes spontaneous, exothermic addition to olefins.
While this problem was not encountered with 1-methylcyclohexene, it is desirable to mix the reagents at
low temperature to avoid a possible vigorous spontaneous reaction and to maximize the yield of adduct.
8. The apparatus should be shielded to avoid exposure to ultraviolet light. The immersion well, lamp,
and the requisite transformer are available from Hanovia Lamp Division, Canrad-Hanovia Inc., 100
Chestnut Street, Newark, NJ 07105. The test tubes are positioned so as to be as close as possible to the
lamp.
9. A "Little Giant" submersible pump (available from Little Giant Pump Co., Oklahoma City, OK) is
used to circulate ice water through the immersion well.
10. The first crop (47.0 g) is followed by two other crops (5.2 and 2.1 g) obtained by concentrating and
cooling the mother liquor.
11. The spectral properties are as follows: IR (KBr disk) cm−1: 2960 (s), 1450 (m), 1380 (s), 1315 (vs),
1205 (s), 1140 (vs), 1090 (vs), 745 (s); 1H NMR (300 MHz, CDCl3) δ: 1.56–1.82 (m, 4 H, CH2), 2.08–
2.41 (m, 4 H, CH2), 2.15 (s, 3 H, CH3), 3.96 (dd, 1 H, CHSO2), 4.58 (AB quartet, 2 H, JAB = 11, CH2Br);
13C NMR (CDCl ) δ: 22.66, 23.25, 24.27, 29.72, 43.69, 44.39, 65.81, 67.21.
3
12. Potassium tert-butoxide can be obtained from Aldrich Chemical Company, Inc.
13. The tert-butyl alcohol and tetrahydrofuran are distilled from calcium hydride prior to use.
14. Warming is required to dissolve the solid in this solvent.
15. The first four washings are done with gentle agitation to avoid emulsion formation.
16. The first cut of the distillate (ca. 1–2 mL) coming below 60°C was discarded.
17. The physical properties of the product are as follows: nD20 1.4722; IR (liquid film) cm−1: 3090 (s),
2940 (s), 2870 (s), 1635 (s), 1440 (s), 895 (vs); 13C NMR (CDCl3) δ: 26.85, 35.37, 107.78, 149.68; GLC
analysis (50 m OV-101 fused silica capillary column obtained from Perkin Elmer, Inc.) showed the
product to be 90–93% pure. The material has an 1H NMR spectrum corresponding to that reported in the
literature:4 (300 MHz, CDCl3) δ: 1.62–1.66 (m, 4 H, CH2), 2.24–2.27 (m, 4 H, CH2), 4.64–4.65 (m, 2 H,
vinyl CH), 4.92–4.93 (m, 2 H, vinyl CH).

3. Discussion
This procedure illustrates a recently published, simple, general method for the synthesis of
conjugated dienes from olefins.5 The scope of the reaction is shown in Table I.5 In most of these
examples hydrogen bromide elimination can be effected by stirring a solution of the olefin–
bromomethanesulfonyl bromide adduct in methylene chloride with 1 equiv of triethylamine at room
temperature. Only 2 equiv of the more costly potassium tert-butoxide are then needed in the second
elimination step; the yields using the two-base procedure are generally superior to that obtained using
only potassium tert-butoxide.

TABLE I
DIENE SYNTHESIS VIA THE VINYLOGOUS RAMBERG–BÄCKLUND REACTION

Olefin Product (Isomer Ratioa) Yield, %b

1 C4H9CH=CH2 C3H7CH=CHCH=CH2 (2:1) 38

2 C6H13CH=CH2 C5H11CH=CHCH=CH2 (2:1)c 61
3 (E)-C4H9CH=CHC4H9 (E)-C3H7CH=CHC(C4H9)=CH2 68d
(E)-C4H9CH=CHC(CH3)=CH2 52
4 (E)-C5H11CH=CHCH3 (E)-C4H9CH=CHC(CH3)=CH2 + CH2=CHC(C5H11)
15
=CH2

5 53

6 74

7 75

8 41e

9 31e

10 49e

11 43>e

12 PhCH2CH=CH2 PhCH=CHCH=CH2 (1:8) 85

13 PhOCH2CH=CH2 PhOCH=CHCH=CH2 (9:1) 54
14 HO(CH2)9CH=CH2 HO(CH2)8CH=CHCH=CH2 (5:1) 86
15 (CH3)3SiCH2CH=CH2 (CH3)3SiCH=CHCH=CH2 (1:10) 41
16 CH2=CH(CH2)6CH=CH2 CH2=CH(CH2)5CH=CHCH=CH2 49f,g,h
17 CH2=CH(CH2)6CH=CH2 CH2=CHCH=CH(CH2)4CH=CHCH=CH2 40i,j
18 (CH3)2Si(CH2CH=CH2)2 (CH3)2Si(CH=CHCH=CH2)2 38i
 a(Z):(E) ratio.
b Overall yield of distilled product.
c(Z):(E) ratios 5:1 and 1:16 from (E)- and (Z)-1-octenylbromomethyl sulfones,

respectively (59–61% overall distilled yields).2

dAnalysis by GLC indicated < 1% (Z)-isomer.
eEt N step omitted.
3
fIsomers not resolved by GLC.
gTwo equivalents of diene used.
hIncludes 5% of 1,3,9,11-dodecatetraene.
iTwo molar equivalents of 1 used.
j 80% (Z.Z).

1,2-Dimethylenecyclohexane, a useful diene for Diels–Alder reactions,6,7,8 has previously been

synthesized in 11–77% yield in multistep procedures from cis-1,2-cyclohexanedicarboxylic anhydride6
or acid,7 from diethyl phthalate,2 or from cyclohexanone.4

References and Notes

1. Department of Chemistry, State University of New York at Albany, Albany, NY 12222. This
work was made possible by grants from the National Science Foundation, the Petroleum
Research Fund administered by the American Chemical Society, the Société Nationale Elf
Aquitaine and the John Simon Guggenheim Memorial Foundation.
2. Bailey, W. J.; Golden, H. R. J. Am. Chem. Soc. 1953, 75, 4780; Blomquist, A. T.; Longone, D. T.
J. Am. Chem. Soc. 1957, 79, 3916.
3. Bost, R. W.; Constable, E. W. Org. Synth., Coll. Vol. III 1943, 610.
4. van Straten, J. W.; van Norden, J. J.; van Schaik, T. A. M.; Franke, G.Th.; de Wolf, W. H.;
Bickelhaupt, F. Recl. Trav. Chim. Pays-Bas 1978, 97, 105.
5. Block, E.; Aslam, M. J. Am. Chem. Soc. 1983, 105, 6164; Block, E.; Aslam, M.; Eswarakrishnan,
V.; Wall, A. J. Am. Chem. Soc. 1983, 105, 6165; Block E.; Aslam, M.; Iyer, R.; Hutchinson, J. J.
Org. Chem. 1984, 49, 3664; Block, E.; Eswarakrishnan, V.; Gebreyes, K. Tetrahedron Lett.
1984, 25, 5469.
6. Bartlett, P. D.; Wingrove, A. S.; Owyang, R. J. Am. Chem. Soc. 1968, 90, 6067.
7. Quin, L. D.; Leimert, J.; Middlemas, E. D.; Miller, R. W.; McPhail, A. T. J. Org. Chem. 1979,
44, 3496.
8. Thummel, R. P.; Cravey, W. E.; Nutakul, W. J. Org. Chem. 1978, 43, 2473.

Appendix
Chemical Abstracts Nomenclature (Collective Index Number);
(Registry Number)

C4H9CH=CH2

C3H7CH=CHCH=CH2

C6H13CH=CH2

(E)-C4H9CH=CHC4H9

(E)-C3H7CH=CHC(C4H9)=CH2
 (E)-C5H11CH=CHCH3

(E)-C4H9CH=CHC(CH3)=CH2

CH2=CHC(C5H11)=CH2

PhCH2CH=CH2

PhCH=CHCH=CH2

PhOCH2CH=CH2

PhOCH=CHCH=CH2

HO(CH2)9CH=CH2

HO(CH2)8CH=CHCH=CH2

(CH3)3SiCH2CH=CH2

(CH3)3SiCH=CHCH=CH2

CH2=CH(CH2)6CH=CH2

CH2=CH(CH2)5CH=CHCH=CH2

CH2=CHCH=CH(CH2)4CH=CHCH=CH2

(CH3)2Si(CH2CH=CH2)2

(CH3)2Si(CH=CHCH=CH2)2

ethanol (64-17-5)

potassium carbonate (584-08-7)

Cyclohexanone (108-94-1)

hydrogen bromide (10035-10-6)

bromine (7726-95-6)

sodium bisulfite (7631-90-5)

Pentane (109-66-0)

methylene chloride (75-09-2)

magnesium sulfate (7487-88-9)

 Tetrahydrofuran (109-99-9)

diethyl phthalate (84-66-2)

1-methylcyclohexene

triethylamine (121-44-8)

tert-butyl alcohol (75-65-0)

calcium hydride (7789-78-8)

tert-BUTYL (1605-73-8)

Bromomethanesulfonyl bromide (54730-18-6)

1,2-Dimethylenecyclohexane,
Cyclohexane, 1,2-bis(methylene)- (2819-48-9)

1-Bromo-1-methyl-2-(bromomethylsulfonyl)cyclohexane (120696-44-8)

1,3,9,11-dodecatetraene

potassium tert-butoxide (865-47-4)

sym-Trithiane (291-21-4)

cis-1,2-cyclohexanedicarboxylic anhydride

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