Sobik et al.
3
6
degradation products of alliin and deoxyalliin from Garlic.
purified by column chromatography with pentane as solvent (12.8
Compound 3 was tested as an oil additive.37 1,2,3-Trithiolane
was recently found by Rushdi and Simoneit who did reactions
with CS2 and oxalic acid solutions in stainless steel vessels at
f
1
3
g, 52 mmol, 52%, R
) 0.2). H NMR (400 MHz, CDCl
): δ [ppm]
1
3
.67 (s, 12H), 3.65 (s, 4H). 13C NMR (100 MHz, CDCl
1.3(CH ), 56.7(CH ), 69.0(C).
Synthesis of 4,4,6,6-Tetramethyl-1,2,5-trithiepane (2). The
3
): δ [ppm]
3
2
high temperature and pressure to get information about the origin
of life.38 A cyclic polysulfide of which conformational studies
synthesized 2-chloro-1-(2-chloro-2-methylpropyldisulfanyl)-2-
methylpropane (0.5 g, 2 mmol) was dissolved in MeOH (10 mL),
and NaSH·xH O (0.11 g) was added in small portions. The solution
2
was stirred at room temperature overnight and was then extracted
with diethyl ether. The solvent was removed after drying with
are well-known is 1,3,5,7-tetrathiocane. Its crystallographic data
39
were published in 1972 and its detailed boat-chair intercon-
version in 1973.40 Published studies of different types of cyclic
4
1
trisulfides including NMR data and rate calculations shows
that the activation enthalpies obtained by us are in a good
agreement.
4
MgSO under reduced pressure. The obtained liquid was purified
by column chromatography with a 200:1 mixture of pentane and
1
diethyl ether (0.1 g, 0.42 mmol, 21%, R ) 0.1). H NMR (400
f
MHz, CDCl
MHz, CDCl
[
3
): δ [ppm] 1.43 (s, 12H), 3.16 (s, 4H). 13C NMR (100
3
): δ [ppm] 31.1 (CH
cm ]: 2959, 2921, 1457, 1409, 1377, 1362, 1101.
Synthesis of 3,3,8,8-Tetramethyl-1,2,5,6-tetrathiocane (6).
3 2
), 52.7 (C), 57.4 (CH ). IR
Experimental Section
-
1
Biological material. The strains were isolated from biofilms
grown on glass plates exposed to the North Sea at a depth of 30
cm for 14 days as described42 and identified by 16S rRNA gene
sequencing.
NaSH·xH O (0.22 g) was dissolved in MeOH (10 mL), and
2
2-chloro-1-(2-chloro-2-methylpropyldisulfanyl)-2-methylpropane (0.5
g, 2 mmol) was added. The solution was stirred at room temperature
over night and was extracted with diethyl ether. The solvent was
Synthesis of 2,2-Dimethylthiirane (10). This compound (bp
8
4-86 °C, 4.84 g, 55 mmol, 79% yield) was prepared according
removed after drying with MgSO under reduced pressure. The
obtained liquid was purified by column chromatography with
4
21
to the procedure of Snyder and Stewart with KSCN (6.79 g, 70
mmol) in 7 mL of H O and 2,2-dimethyloxirane (5.04 g, 70 mmol).
H NMR (400 MHz, CDCl ): δ [ppm] 1.62 (s, 6H), 2.40 (s, 2H).
): δ [ppm] 28.5(CH ), 35.4(CH ), 42.4-
2
Pentane as solvent (0.12 g, 0.5 mmol, 25%, R ) 0.15). Mp.: 71
f
1
1
3
( 0.5 °C. H NMR (400 MHz, CDCl ): δ [ppm] 1.23 (s, 6H),
3
1
3
C NMR (100 MHz, CDCl
C).
3
3
2
1.34 (s, 6H), 3.06 (d, J ) 15.2 Hz, 2H), 3.70 (d, J ) 15.2 Hz, 2H).
13
(
3 3 3
C NMR (100 MHz, CDCl ): δ [ppm] 25.2(CH ), 32.2(CH ), 51.1-
-
1
Synthesis of 3,3,7,7-Tetramethyl-1,2,5-trithiepane (3) and
(C), 53.9(CH ). IR [cm ]: 2953, 2896, 1377, 1358, 1090. Anal.
8 16 4
calcd. for C H S : C, 39.96%; H, 6.71%; S, 53.34%. Found: C,
2
3,3,6,6-Tetramethyl-1,2,5-trithiepane (4). In a three-necked round-
bottom flask, 7 equiv of NaSH·xH
2
O (21.56 g) was dissolved in
00 mL of MeOH, and triethylamine (0.56 g, 5.5 mmol) was added.
40.04%; H, 6.55%; S, 53.32%.
Synthesis of 2-Methyl-1,2-propanedithiol (8). The crude 4,4-
dimethyl-1,2,3-trithiolane (1.5 g), coproduct in the synthesis of
2
Then 2,2-dimethylthiirane (4.84 g, 55 mmol) was added dropwise
during 30 min. The solution was stirred at room temperature. After
4,4,6,6-tetramethyl-1,2,5-trithiepane and 3,3,8,8-tetramethyl-1,2,5,6-
2
days, water was added and the mixture extracted three times with
tetrathiocane, was added to a large excess of LiAlH (2 g, 52 mmol)
4
diethyl ether. The solvent was removed after drying with MgSO
under reduced pressure. The obtained liquid was purified by column
chromatography with pentane and 3,3,7,7-tetramethyl-1,2,5-trithi-
4
in absol diethyl ether. The solution was boiled at 45 °C for 3 h and
hydrolyzed by addition of concd HCl until all solids dissolved. The
aqueous layer was extracted several times with diethyl ether. The
combined organic layers were dried with MgSO and filtered, and
4
the solvent was removed. The crude product was finally purified by
epane (3) (1.2 g, 5.8 mmol, 11%, R
f
) 0.15) obtained as a pale
yellow solid. Mp: 46 ( 0.5 °C. H NMR (400 MHz, CDCl ): δ
ppm] 1.27 (s, 6H), 1.47 (s, 6H), 2.81 (dd, J ) 2.3, 17.2 Hz, 4H).
1
3
[
distillation to yield pure 8 (0.7 g, 5.7 mmol) (40-41 °C, 38 mmHg).
1
3
C NMR (100 MHz, CDCl
3
): δ [ppm] 27.0 (CH
3
), 28.2 (CH
), 52.4 (C). IR [cm ]: 2952, 1443, 1360, 1139, 1093.
Anal. calcd for C : C, 46.11%; H, 7.74%; S, 46.16%.
Found: C, 45.86%; H, 7.34%; S, 45.91%. 3,3,6,6-tetramethyl-1,2,5-
trithiepane (4) (0.9 g, 4.3 mmol, 8%, R ) 0.12). Mp: 34 ( 0.5
): δ [ppm] 1.33 (s , 12H), 2.55
, 1H), 2.92 (s, 2H), 3.15 (s
, 1H). 13C NMR (100 MHz,
CDCl ): δ [ppm] 25.9(CH ), 27.1(CH ), 29.9(CH ), 30.9(CH ),
1.5(CH ), 45.6(C), 55.6(C), 57.7(CH ). IR [cm ]: 2957, 1441,
375, 1137, 1093.
3
),
1
H NMR (400 MHz, CDCl ): δ [ppm] 1.43 (s, 6H), 1.61 (t, J )
3
-
1
5
0.2 (CH
2
13
8
.8 Hz, 1H), 2.02 (s, 1H), 2.75 (d, J ) 8.8 Hz, 2H). C NMR
100 MHz, CDCl ): δ [ppm] 30.25 (CH ), 41.21 (CH ), 45.12 (C).
Synthesis of 3,3,7,7-Tetramethyl-1,2,5,6-tetrathiocane (5). To
a mixture of NaOH (0.4 g, 10 mmol) and KI (10 mg, 0.06 mmol),
dissolved in H O (10 mL) and cooled in an ice-bath to 0 °C, was
added 2-methyl-1,2-propanedithiol (0.6 g, 5 mmol) dropwise, and
the solution was stirred for 30 min. Than I (1.27 g, 5 mmol) was
added portionwise until a light red color persisted. The solution
was extracted with dichloromethane. After drying with MgSO , the
8 16 3
H S
(
3
3
2
f
1
°
(
C. H NMR (400 MHz, CDCl
3
B
2
s
B
B
3
3
3
3
3
2
-
1
4
1
2
2
4
Synthesis of 2-Chloro-1-(2-chloro-2-methylpropyldisulfanyl)-
solvent was removed under reduced pressure by column chroma-
tography with pentane, yielding a pale yellow solid (0.26 g, 1.1
2-methylpropane (11). Isobutene (5.6 g, 0.1 mol) was condensed
into a round-bottom flask, cooled with liquid nitrogen, and than
dissolved in dichloromethane at -40 °C. S Cl (0.5 equiv, 6.75 g,
.05 mol) was added and stirred for 60 min at -40 °C, followed
by 2 h of stirring at room temperature. The solvent and the excess
of S Cl were separated by distillation. The obtained liquid was
1
mmol, 23%, R
CDCl ): δ [ppm] 1.35 (s
CDCl ): δ [ppm] 56.3(C). IR [cm ]: 2953, 1450, 1363, 1134,
091, 548.
f
) 0.1). Mp: 106 ( 0.5 °C. H NMR (400 MHz,
2
2
13
3
B B
,12H), 3.17 (s , 2H). C NMR (100 MHz,
0
-1
3
1
2
2
Acknowledgment. Financial support was provided by the
Volkswagenstiftung within the Marine Biotechnology Project
in Lower-Saxony (Germany).
(
36) Kubec, R.; Velisek, J.; Dolezal, M.; Kubelka, V. J. Agric. Food
Chem. 1997, 45, 3580-3585.
37) Umanskaya, O. I.; Abadzheva, R, N.; Yaniv, A. A. Neftyanaya i
(
GazoVaya Promyshlennost 1984, 2, 52-53.
(
38) Rushdi, A. I.; Simoneit, B. R. T. Astrobiology 2005, 5, 749-768.
Supporting Information Available: The methods and instru-
ments as well as the spectral data of the compounds 1-3, 5-8,
(39) Gerard, W. F.; Degen, P. J.; Anet, F. A. L. J. Am. Chem. Soc. 1972,
9
4, 4792-4793.
40) Gerard, W. F.; Degen, P. J.; Anet, F. A. L. Acta Crystallogr. B
1
0, and 11, a table with the HRMS data of the compounds A-E,
(
1
973, 29, 1815-1822.
and XY data of calculated structures. This material is available free
of charge via the Internet at http://pubs.acs.org.
(
(
41) Friebolin, H.; Mecke, R. Z. Naturforsch. 1966, 21, 320-324.
42) Allgaier, M.; Uphoff, H.; Wagner-D o¨ bler, I. Appl. EnViron. Micro-
biol. 2003, 69, 5051-5059.
JO070048W
3782 J. Org. Chem., Vol. 72, No. 10, 2007