124
NOTES
Vol. 65
TABLEI THALLOUS SULFONATES Thallous
oc 139-140 2 13-2 1tj 226-2223 274-276 307309 207-209 220-222 101-103 228-232 dec 267-269 260-262 2%-285 340-341 dec. 21 p
58lt
Sulfamate o- Toluenesulfonaie p-Toluenesulfonate p-Bromobenzenesulfonate m-Nitrobenzenesulfonate Sulfanilate 2-Bromotoluene-4-sulfonate 2-Aminotoluene-4-sulfonate 2-Naphthoquinone-4-sulfonat e d-Camphorsulfonale 1,2,3,4-Tetramethylbenzene-5-sulfonat es 1,2,3,5-Tetramethylbenzene-4-sulfonateb 1,2,4,5-Tetramethylbenzene-3-sulfonate~ Pentamethylbenzenesulfonate&
(4) Meyer and Bertham, Ber , 97, LO61 (1904) (6) The authors wish to thank Ur I, I Smith for sample5 of t h e w sodium sutfonate5 T h e melting points reported in Table I are iin corrected
AMES, IOWA
KFCFIVED OCTOBER 26, 1942
The Catalytic Reduction of Dehydrocholic Acid in Presence of Raney Nickel BY
HzOaNSTI C7H7O&Tl C7H70sST1 CsHaOaBrSTl GHiOsNSTl CsHeOaNSTl C7H80gBrSTl CiHsOaNSTl CioH~09Tl CioHibOrSTl CioHi30aSTl CioHiaOsSTl CioHiaOaSTl
68.0 54.3 54.3 46.3 50.3 54.3 44.8 52.3 47.9 46.8 49.0 49.0
68.0 54.3 54.1 46.3 50.2 54 2 44.5 52.1 47.6 46.6 48.7 48.9 48.8
49.0
:325-326
The sulfonic acid is readily regenerated from the thallous salt by acidification with hydrochloric acid.
CHEMICAL LABOKATOKI COLLEGE IOWASTATE
T I analyses, yo' Calcd Found
Formula
w. 5'1.HOEHSA S D H. E. T!K:C,hTADP
Dehydrocholic acid has been reduced with palladium and hydrogen in acetic acid, with aluminum amalgam with benzene and ether as the solventll with sodium amalgam2 and electrolytically.3 Ethyl dehydrocholate has been reduced with hydrogen in the presence of a catalyst consisting of nickel or cobalti Biological systems also have been studied and it has been found that reductodehydrocholic acid,6 isoreductodehydrocholic acid6ei and 7hydroxy-3,12-diketocholanicacidqgwere formed from dehydrocholic acid. I t has now been found that reductodehydrocholic acid is the. main product when dehydrocholic acid is reduced in methanol solution with
hydrogen in the presence of Raney nickel. Other compounds that have been isolated from the rnixture were methyl dehydrocholate and methyl reductodehydrocholate. Yields of reductodehydrocholic acid as high as 85% of the theoretical amount may be obtained when the reduction of dehydrocholic acid in methanol solution is carried out a t 1 0 5 O , under a hydrogen pressure of 3800 Ib. No further reduction of reductodehydrocholic acid was observed when i t was submitted to a hydrogen pressure of 5800 Ib. at a temperature of 230". Two typical runs are listed in the following table Moles of dehydrocholic acid
?', *C
P
Time, hr.
0 1
110
3800
3
(1 2
10.5
3800
;i
Products isolated
67% reductodehydrocholic acid 20% methyl reductodehydrocholate 12% methyl dehydrocholate 85% reductodehydrocholic acid 5% dehydrocholic acid 10% mixture of esters
Physical constants of the pure compounds Reductodehydrocholic acid, 111. p 187-188" [a]"D
+30 * i
=
Methyl dehydrochdate, m p. 232-233' f30
*
1
[CX]~~ =D f32
*
1
[a]"D
(1) Borsche and Hallwass. B e r . , 66, 3318 (1922) (2) Schenck, Z . physiol. Chem., 69,383 (1910). (3) Schenck, ibid., 63, 308 (1909). (4) Bockmuhl, Ehrhart and Ruschig, U . S. Patent 2,143,676 (1939). (5) Kyoguku, 2. Qhusiol. Chem., 250, 258 (1937). (6) Shibuya, J . Biochem. (Japan), 17, 385 (1933). (7) Yamosaki and Kyoguku, Z . physiol. Chem.. 233, 29 (1935): 286, 443 (1935). ( 6 ) Mori. .I. Uiarhcm !.rapan) 29, X i 'lW'.i'
Methyl reductodehydrocholate, m.p. 152-153
O
GEORGE BREON& Co. RESEARCH LABORATORIES KANSASCITY,MISSOTJRX CHEMISTRY DEPARTMENT UNIVERSITY OF MISSOURI MISSOURI RECEIVED NOVEMBER 4, 1942 COLUMBIA.
