5832
JOHN
K. E. HOOVER AND ALLAN K. UAY TABLE I
PROPERTIES OF
2-BENZIMIDAZOLYLTHIO
flCIOS
H
Ring aubstitu tion 3 Chloro5-Chloro5-Chloro4,6-Dichloro5,6-Dichloro5,6-Dichloro4,5,6-Trichloro4,5,6-Trichloro5-Bromo5-Bromo&Nitro5-Nitroj-hfethoxyl5-Llethoxyl5-Methyl5-LIethyl4,6-Dimethyl4,6-Dimethyl5,6-Dimethyl5,6-Dimethyl5.Phenyl5-Phenyl-
Acid side chain a-Propionic Acetic @-Propionic a-Propionic Acetic Acetic a-Propionic Acetic a-Propionic Acetic a Propionic Acetic a-Propionic Acetic a-Propionic Acetic a-Propionic Acetic a-Propionic Acetic a-Propionic Acetic a-Propionic
RI p . . n O C
181-182 193-194 103-108 166-167 222-224 21 9-221 230-231 205-207 222-224 194-196 180-181 191-192 186-188 194-196 1 31-152 197-200 160-162 247-249 160-161 207-209 208-210 215-216 200-202
Yie1d.b Formula % C I Q H I Q O Z X ~ S 41 C P H ~ O Z N Z S C I 68 C I Q H U O Z N Z S C ~ 60 C I Q H U O Z N Z S C ~ 39 CQHEOZNZSCIZ 25 CQHBOZXZSCIY 81 C I O H E O Z X Z S C ~ Z159 42 C~Hs0zNzSCla C I O H ~ ~ Z ~ - Z S 80 C~D 70 CeH70zNzSBr 43 C!oHQOzNzSBr ti9 CgHiOiXaS 32 CioH7OiNaS 30 CIQHIDOIN~S 71 CUHI~OJNZS 4i OIOHIQOZ?;ZS CIIHIZOZX~ZS .),I CiiHizOzNzS UI CIZH!IOZSZS 8 .i CuHi20zKzS C I Z H I ~ O ~ N Z S 64 C I ~ H L ~ O Z N Z S 74 87 CIEHIIO1NZS
_ .,__ ., _
Neut. eyuiv. Calcd. F o u n d 222.3 218.8 242.7 245.5 256.7 259.0 256.7 253.0 277.1 277.3 277.1 274.1 291.2 292.3 311.6 310.2 325.6 324.4 287.1 288 1 302.4 301.2 2.53.2 230 .5 271.0 26i.3 235.7 238.3 255 1 252.3 226.4 222.3 23G. 3 240.3 231.7 236.3 250.3 248.2 236.3 234.9 233 7 2.50. 3 284.3 282.8 298.4 207). 4
Carbon, % Hydrogen, Calcd. Found Calcd. Found 24.01 33.87 4.54 4.48 44.67 44.54 2.91 3.25 46.78 46.58 3.53 3.73 46.78 46.55 3.53 3 43 3 9 . 0 0 3iJ.34 2.18 2 36 39.00 39.38 2.18 2.41 41.25 41.28 2.77 3.02 34.69 3-4.75 1.ii2 1.89 36.88 37.09 2.17 2.11 RY8G 2.46 2.68 37.64 3!1.43 3.01 2.SU 30.88 -12 68 42.54 2.79 2.90 44 9 4 45 03 3.39 3.13 50.41 30.79 4.23 4.21 .52 36 52.63 4 . 7 9 4.85 ,54. 04 31.00 4.54 4.62 35.91 56.09 5.12 5.47 55.g1 56.01 5,12 4.92 57.58 57.68 5.G4 5 . 9 9 ,5;7, 91 5.7.74 5.12 5.33 57.58 57.97 A.64 S.91 63.3ti 63.40 4.25 4.21 64.41 F4.16 4.73 4.52 ~~
Nitrogen, 5; Calcd. Found 12.60 12.72 11.54 11.23 10.01 10.88 10.01 10.92 in.11 10.00 10.11 1 0 08 9.62 !>.e!) 8 . I)!) 2.33 8.60 8 . 8'1 9 .i f i 9.84 0.30 9.45 6.31 6.59 5.90 5.72 1.77 1.76 1.07 1.10 3.61 2.60 1.71 1.86 11.86 11.85 11.19 10.98 11.86 12.11 11.19 11.32 9.85 9.79 9.39 9.35
The melting points were determined 0.1 a Fishtr-John5 melting point block aud corrected for calibration of the instrument. * Yields are calculated on the basis of the once-recrystallized acid. 2 - Nitro - 4 - methoxyaniline, 4 - amino - 3 - nitrobiphenyl, 4inet h yl-2-nitroadhe and 2,4-dimethyl-6-nitroaniline, respectively, by reduction with stannous chloride in concentrated hydrochloric acid. 1,3-Dichlor0-2,5-diaminobenzene,~~ 4l~romo-l,2-diamin0benzene~~ and 4,5-dimethyl-l,2-diaminohenzene'5 were synthesized from 2,4-dichloroaniline, nzbromoaniline and 3 ,Cdimethylaniline, respectively, by nitrating the acetylated aniline derivative with concentrated nitric x i d and reducing the nitro compound after hydrolysis with (13) 0 . N. W i t t , Der., 7, l G O l (1874). (14) H . H u b n e r , A n n . . 209, 339 (1881). (15) E. Noelling, A. Braun a n d G. Thesmar, Be i... 34, 2 2 2 2 11901).
1.1C U N ? . K t U I I I
stannous chloride. 1,2-Dichlor0-4,5-diaminobenzene~~ was made from 12-dichloro-2-nitrobenzene by nitration and reductioii of the dinitro compound'7 with mossy tin in concentrated hydrochloric acid. 1,2,3-Trichloro-5,6-diaminobenzene was prepared by the reduction of 1,2,3-trichloro-5,6dinitrobenzene'* which in turn was synthesized by the nitration of 1,2,3-trichlor0-5-nitrobenzene.~~ EAST LANSING, MICHIGAX (16) D . U . Woolley, E . A. Singer a n d K. S m i t h , J . E z p f l ,\Tr
