From Wikipedia, the free encyclopedia
Chemical compound
1,3,5-Trithiane
|
|
Names
|
Preferred IUPAC name
|
Other names
Thioformaldehyde trimer, Trimethylentrisulfide, Trimethylene trisulfide, Trithioformaldehyde, 1,3,5-Trithiacyclohexane,
sym
-Trithiane, Thioform,
s
-Trithiane
|
Identifiers
|
|
|
|
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ChEBI
|
|
ChemSpider
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ECHA InfoCard
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100.005.482
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EC Number
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UNII
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InChI=1S/C3H6S3/c1-4-2-6-3-5-1/h1-3H2
Y
Key: LORRLQMLLQLPSJ-UHFFFAOYSA-N
Y
InChI=1/C3H6S3/c1-4-2-6-3-5-1/h1-3H2
Key: LORRLQMLLQLPSJ-UHFFFAOYAA
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Properties
|
|
C
3
H
6
S
3
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Molar mass
|
138.27
|
Appearance
|
Colourless solid
|
Density
|
1.6374 g/cm
3
[1]
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Melting point
|
215 to 220 °C (419 to 428 °F; 488 to 493 K)
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Slightly soluble
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Solubility
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Benzene
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Hazards
|
Occupational safety and health
(OHS/OSH):
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Main hazards
|
Toxic (
T
)
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GHS
labelling
:
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|
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Warning
|
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H319
|
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P264
,
P280
,
P305+P351+P338
,
P313
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NFPA 704
(fire diamond)
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Except where otherwise noted, data are given for materials in their
standard state
(at 25 °C [77 °F], 100 kPa).
|
Chemical compound
1,3,5-Trithiane
is the
chemical compound
with the
formula
(CH
2
S)
3
. This
heterocycle
is the cyclic
trimer
of the otherwise unstable species
thioformaldehyde
. It consists of a six-membered ring with alternating
methylene bridges
and thioether groups. It is prepared by treatment of
formaldehyde
with
hydrogen sulfide
.
[2]
Trithiane is a building block molecule in
organic synthesis
, being a masked source of
formaldehyde
. In one application, it is deprotonated with organolithium reagents to give the lithium derivative, which can be
alkylated
.
[3]
- (CH
2
S)
3
+ RLi → (CH
2
S)
2
(CHLiS) + RH
- (CH
2
S)
2
(CHLiS) + R
′
Br → (CH
2
S)
2
(CHR
′
S) + LiBr
- (CH
2
S)
2
(CHR
′
S) + H
2
O → R
′
CHO + ....
Trithiane is the dithioacetal of formaldehyde. Other
dithioacetals
undergo similar reactions to the above.
It is also a precursor to other
organosulfur
reagents
. For example, chlorination in the presence of water affords the chloromethyl
sulfonyl chloride
:
[4]
- (CH
2
S)
3
+ 9 Cl
2
+ 6 H
2
O → 3 ClCH
2
SO
2
Cl + 12 HCl
Trithianes
[
edit
]
Trithiane is the parent of a class of heterocycles called
trithianes
, that formally result from substitution of various
monovalent
groups
for one or more of the hydrogen atoms. The species often arise from thiation of ketones and aldehydes. The incipient
thioketones
and
thioaldehydes
undergo
trimerization
. One example is
2,2,4,4,6,6-hexamethyl-1,3,5-trithiane
, or trithioacetone, the trimer of
thioacetone
(propane-2-thione). Alternatively 1,3,5-trithiane can be deprotonated and alkylated to afford (SCH
2
)
n
(SCHR)
3-n
.
[5]
The conformation of trithianes has been well investigated.
[6]
References
[
edit
]
- ^
David R. Lide, ed.
Handbook of Chemistry and Physics, 85th Edition
, Internet Version 2005. CRC Press, 2005.
- ^
Bost, R. W.; Constable, E. W. "sym-Trithiane" Organic Syntheses, Collected Volume 2, p.610 (1943).
http://orgsyn.org/Content/pdfs/procedures/CV2P0610.pdf
- ^
Seebach, D.; Beck, A. K. "Aldehydes From
sym
-Ttrithiane:
n
-Pentadecanal" Organic Syntheses, Collected Volume 6, p.869 (1988).
http://orgsyn.org/Content/pdfs/procedures/CV6P0869.pdf
- ^
Paquette, L. A.; Wittenbrook, L. S. "2-Chlorothiirane 1,1-Dioxide" Organic Syntheses, Collected Volume 5, p.231 (1973).
http://orgsyn.org/Content/pdfs/procedures/CV5P0231.pdf
- ^
Edema, Jilles J. H.; Hoogenraad, Marcel; Schoonbeek, Franck S.; Kellogg, Richard M.; Kooijman, Huub; Spek, Anthony L. (2010). "Alkylation of the SCS linkage. Towards lipophilic mono- and ditopic heavy-metal receptors containing trithiane building blocks. Molecular structure of cis-2,4,6-tribenzyl-1,3,5-trithiane".
Recueil des Travaux Chimiques des Pays-Bas
.
112
(6): 370?375.
doi
:
10.1002/recl.19931120611
.
- ^
Breslow, David S.
; Skolnik, Herman (2009). "C3S3 Ring Systems".
Multi-Sulfur and Sulfur and Oxygen Five- and Six-Membered Heterocycles, Part 2
. Vol. 21. John Wiley & Sons. p. 689.
ISBN
978-0-470-18833-0
.