POTASSIUM HYDROGEN SULFIDE

Potassium Hydrogen Sulfide

KSH

[1310-61-8]
HKS
(MW 72.18)
InChI = 1/K.H2S/h;1H2/q+1;/p-1/fK.HS/h;1h/qm;-1
InChIKey = ZOCLAPYLSUCOGI-QTJLXTHTCK

Thiocarbonyl Compounds.3 In general, KSH and NaSH are

interchangeable with respect to their use in the generation of the
thiocarbonyl functional group. The thiolysis of benzotrichloride
yields the potassium salt of dithiobenzoic acid, an intermediate in
the preparation of thiobenzoylthioglycolic acid, a useful thiobenzoylating agent (eq 4).4a Other trichlorides behave similarly.
O
Et
2 mol

(a nucleophile and reducing agent similar to NaSH; useful in the

synthesis of thiols,1 thioethers,2 and thiocarbonyl compounds3 )
Physical Data: mp 455 C; d 1.681.70 g cm3 .
Solubility: very sol H2 O; sol EtOH.
Form Supplied in: commercially available as a crystalline solid;
colorless when pure. May be contaminated with K2 S2 O3 and
K2 CO3 .
Preparative Method: saturation of ethanolic KOH by H2 S.4
Handling, Storage, and Precautions: extremely hygroscopic.
Darkens on heating to yellow, then deep red at mp. Aqueous so
KOH + H2 S), and
lutions evolve H2 S on heating (KSH + H2 O 
decompose in air to polysuldes and H2 S. Oxygen also yields
K2 S2 O3 and traces of K2 SO3 . Carbon dioxide yields H2 S and
K2 CO3 . For other precautions and toxicity see Sodium Hydrogen Sulfide.

Thiols.1 Yields from organic halides may be less satisfactory than with NaSH because of formation of greater amounts of
thioether with KSH.5 The amount of thiol may be increased at
the expense of the thioether by addition of Hydrogen Sulfide or
Sulfuric Acid Phase transfer catalysis is useful (eq 1).6

PhCH2Br + KSH

MeO(CH2CH2O)79Me
C6H6, 23 C
30 min
73%

<20% without catalyst

1. KSH (H2S + KOH)

EtOH, 0 C

O
O

2. HCl
100%

SH

Thioethers (Sulfides).2 As noted above, thioether formation

from organic halides occurs to a greater extent with KSH than with
NaSH. Modest yields (1550%) of suldes are obtained, along
with polymers, by Michael addition of KSH to ,-unsaturated
ketones or sulfones generated in situ from ketone or sulfone and
formaldehyde (eq 3).9

O
S

48.8%

(3)

0.5 mol 1.23 mol

KSH (H2S, KOH, EtOH)

60 C, 11.5 h

PhCS2K

1. ClCH2CO2Na
H2O, reflux, 5 min
2. HCl

S
CO2H
5457%

(4)

Miscellaneous. Treatment of 2-alkoxy-2-oxo-1,3,2-dioxaphospholanes with KSH gives a phosphodiester with a -mercaptoethyl group that functions as a protective group easily removed
by treatment with base (eq 5).10 The S-substituted derivatives are
more useful as protective groups since they are stable to bases as
well as acids.

t-Bu

t-Bu

O
O
P
O
O

KSH (H2S, t-BuOK)

t-BuOH, rt, 3 h
93%

O
P O
O
O K+

NaOH, H2O
(on Me3NH+ salt)
C2H4S
87%

t-Bu

O
P ONa (5)
O
ONa

Related Reagents. Bis(trimethylsilyl) Sulde; Hydrogen

Sulde; Sodium Hydrogen Sulde; Sodium Sulde.

1.

Gundermann, K.-D.; Hmke, K., Methoden Org. Chem. (Houben-Weyl)

1985, E11, 32.

2.

Gundermann, K.-D.; Hmke, K., Methoden Org. Chem. (Houben-Weyl)

1985, E11, 158.

3.

(a) Voss, J., Methoden Org. Chem. (Houben-Weyl) 1985, E11, 188.
(b) Mayer, R.; Scheithauer, S., Methoden Org. Chem. (Houben-Weyl)
1985, E5, 891. (c) Bauer, W.; Khlein, K., Methoden Org. Chem.
(Houben-Weyl) 1985, E5, 1218. (d)Schaumann, E. The Chemistry of
Double Bond Functional Groups, Supplement A, Patai, S., Ed.; Wiley:
New York, 1989; Vol. 2, Part 2, p 1269.

4.

(a) Kurzer, F.; Lawson, A., Org. Synth., Coll. Vol. 1973, 5, 1046.
(b) Noble, P. Jr.; Tarbell, D. S., Org. Synth., Coll. Vol. 1963, 4, 924.
(c) Frank, R. L.; Blegen, J. R., Org. Synth., Coll. Vol. 1955, 3, 116.
(d) Zinner, H., Biochemistry 1953, 86, 825.

5.

Ref.1, p 34.

(2)

NH2

Ph

H2O
rt, 8 d

(1)

Thiocarboxylic Acids.7 Thiobenzoic acid (PhCOSH) is obtained in 6176% yield by addition of Benzoyl Chloride to ethanolic KSH;4b it is an intermediate in the preparation of benzoyl
disulde.4c Anhydrides (eq 2)8 and esters also are suitable.

N
H

PhCCl3

+ KSH + CH2O

SH
PhCH2SH

Avoid Skin Contact with All Reagents

POTASSIUM HYDROGEN SULFIDE

6. Lehmkuhl, H.; Rabet, F.; Hauschild, K., Synthesis 1977, 184.

7. Bauer, W., Khlein, K., Methoden Org. Chem. (Houben-Weyl) 1985, E5,
832.
8. Fanning, A. T. Jr.; Bickford, G. R.; Roberts, T. D., J. Am. Chem. Soc.
1972, 94, 8505.
9. (a) Dronov, V. I.; Nigmatullina, R. F.; Khalilov, L. M.; Nikitin, Yu. E.,
J. Org. Chem. USSR (Engl. Transl.) 1980, 16, 1196. (b) Dronov, V. I.;

A list of General Abbreviations appears on the front Endpapers

Nigmatullina, R. F.; Makhmutova, I. Kh.; Nikitin, Yu. E., J. Org. Chem.

USSR (Engl. Transl.) 1982, 18, 468.
10. Thuong, N. T.; Chassignol, M.; Asseline, U.; Chabrier, P., Bull. Soc.
Chem. Fr., Part 2 1981, 51.

Donald C. Dittmer
Syracuse University, Syracuse, NY, USA