摘要:

Vogel and Cowaia 8. Physical Properties and Chemical Constitution. Part VII. Alkyl Sulphides Disulphides Sulphites Xulphates and Orthophosphates. By ARTHURI. VOGEL and DAVIDM. COWAN. The refractive indices for the C D F and G' lines at 20*0",and the surface tensions and densities over a range of temperatures have been determined for numerous alkyl compounds particularly sulphides and disulphides. The molecular refractivities and parachors have been evaluated. The data obtained have been employed in the calculation of preliminary values for the constants of sulphur and for the contribution of the oxygen atom in alkyl sulphites and sulphates. THE literature contains but few trustworthy experimental results from which the physical constants (refractivities molecular refraction coefficient and parachor) of sulphur may be deduced (compare Eisenlohr " Spektrochemie organischer Verbindungen," 1912 pp.64 et seq. ; Sugden Reed and Wilkins J. 1925 127 1533; Baroni Atti I?. Accad. Lincei 1931 14 28; Bezzi Gazzetta 1935 65 693). The most satisfactory method for evaluating the constants for sulphur is from dialkyl sulphides new data for a comprehensive series of such compounds are now presented. Since trustworthy figures for carbon and hydrogen are not available (largely because of the uncertainty of the CH value) the necessary calculations will be made in a future communication. For the present attention is directed to the following results for the various isomeric sulphides.* Isomeric A lkyl Sulphides. P. RC. RD. RF.ROT. Mn?". MeBuaS .............................. 280.1 32-92 33.10 33-53 33.94 150-93 RZeBuBS .............................. 279.6 32-99 33-17 33.60 33.93 150.41 MeBuYS .............................. 277.9 33-10 33-29 33.73 34.08 150.14 EtBuaS .............................. 320.3 37.68 37-89 38.38 38.75 171.29 EtBuYS .............................. 31 7.2 37.93 38.12 38-63 39-02 170.44 Bua,S ................................. 399.3 46-82 47.06 47.64 48.10 212.54 Bub,S ................................. 395.4 47-04 47-29 47-90 48.32 21 1.65 sec.-Bu,S ........................... 395.0 46-90 47-14 47.74 48.19 212.19 * For significance of abbreviations in the Table see p. 18. [19431 Physical Yroperties and Chemical Constitution. Part VII.The facile conversion of thiols into disulphides by means of iodine 2RS- + I = RSS-R (I.) + 21- would seem to support formula (I)for disulphides (compare X-ray studies of Egartner Halla and Schacherl 2.physikal. Chem. 1932 B 18 189). By subtracting the experimental values for sulphides from those of disulphides a direct determination of the sulphur contribution is obtained. The results are collected below. This of course will correspond to linkages of the type C*S*Sand may not be identical with C-S-C (deducible from alkyl sulphides alone) (compare Smyth '' Dielectric Constant and Molecular Structure," 1931 p. 162). Values for Sulphur (R3,-RZS). R. P. RC. RD. RF. RG~. Mnr. Methyl .............................. 50.8 7.95 8-02 8.2 1 8.39 54.53 Ethy1 ....... . . . ..... . . ..... . . . . . . .. . .. 4 9 -6 8.05 8.14 8-30 8.45 54.13 n-Propyl . . .. . .. . ..... . ... . .. . . .. . . . 49.6 8-04 8.11 8-30 8.47 53.85 isoPropy1 ...... . ......... . . . ..... . .. 50.1 8.02 8.06 8-28 8-42 53-98 n-Butyl .............................. 48.4 8.10 8.15 8.35 8.49 53.65 isoButyl ........................... 48.0 7-90 7-98 8.14 8.33 53-49 n-Amy1 .... . . . . . . . .. . . . . . .. . ,. . .. . . ,. 47* 6 8.12 8.21 8.41 8.57 53.44 isoAmyl .............................. 48.3 7-97 8-04 8-23 8.41 53.53 Mean ................................. 49.1 8.019 8.089 8.278 8.441 53-78 The results for isomeric disulphides are presented in the next table. Isomeric ,4 lkyl Disulphides. P. Rc. RD. RF. Roe. Mn:'. Bua2S2.... ... . . . . . . . ... . . . .... . ... . .. 44'7.7 64-92 65.21 55.99 56.59 266-19 Bup,S ............................... 443.4 34.94 35.2'7 56-04 56-65 265.14 BuY,S .... . ...,..,.... . ........ . . . . . . 440.9 65-54 55-87 56-68 57.31 265-73 In order to provide information as to the nature of the linkage in sulphites and sulphates measurements have been made on alkyl sulphites and sulphates. By comparison with the corresponding sulphides (R,SO -R,S and R,SO -R,S) the contribution of the oxygen atom may be calculated. The final results are in the following tables. Contribution of the Oxygen Atoin in Alkyl Sulphites (R,SO -R,S)/3. R. P. RC. RD. RF. RG.. Mn2,o'. Methyl ... . ...... . . .. . . . . ..... . . .... . 18.9 1.113 1.110 1.103 1.097 22-00 Ethyl .. ......... . . .. .......... . . .. .... 18-7 1.123 1.127 1.107 1.097 21-79 92-Propyl . .. . .. . . . ... . ....... . ...... 18.8 1.167 1.167 1.157 1.147 21-82 isoPropy1 . . . . . . ,. . . . . . . .... . . . .. . . . . 18.9 1.090 1.077 1-073 1.057 21.66 n-ButyI .. . ......... . . .. . . . .... . . . . . . . 18.1 1-147 1.150 1.140 1.123 20.98 isoButy1 . . . . .. . . ..... . . . .. . .. . . . . . . 18.4 1.093 1.090 1.073 1.073 21.86 n-Amy1 .............................. 18.3 1.143 1.140 1.140 1.120 21.82 isoAmyl .............................. 17.9 1.087 1-080 1-070 1.060 21.96 Mean ....... . . . . . ..... . . ... . . .. . .. . . .. 18.5 1.120 1.118 1.108 1-097 21-74 Contribution of the Oxygen Atom in Alkyl Sulphates (R,SO -R,S)/4. Methyl . .. . ................. . . . . .. . .. 18.7 0-818 0.813 0-790 0.7'75 21.45 Ethyl .................... ............. 18.7 0.815 0.810 0.780 0,758 2 1-46 n-Propyl .. . . . . . . . .. . . ..... . . . ... . . . 18.3 0.800 0.793 0.768 0-745 21-57 n-Butyl .............................. 17.9 0.808 0.800 0.775 0.763 21.58 Mean .. . . . .... . . .. . . .. . . ... . . .. . .. . . . . 18.2 0.810 0.804 0-778 0-758 21-52 The low values for the refractivities as well as their decrease in the series Rc -+ Rot are noteworthy [compare e.g. R,,for 0 (carbonyl) 2.211 0 (ether) 1.643 0 (hydroxyl) 1.525; Eisenlohr op. cit. 1912 p. 48; Z. physikal. Chem. 1911,75,5851 these provide new evidence for co-ordinate links in sulphites and sulphates. The subject will be discussed in detail particularly from the viewpoint of the refraction of election groups (von Steiger Bey.1921 54 1381; Smyth Phil. A!Tag. 1925 50 361; op. cit. p. 150; Fajans and Knorr Ber. 1926 59,249) in a later communication. Measurements upon trialkyl orthophosphates have also been made but detailed parallel calculations cannot be given because suitable data on the constants of phosphorus are lacking. However from the scanty refractivity data available [RDfor PEt at 18.6" (Zecchini Gazzetta 1893 23,97 ; 1894 24 34); Rc R, and RFfor PPrQ and PBua at 25" (Jones Davies and Dyke J. Physical Chevn. 1933 37,584)] analogous results are obtained (see below). Contribution of the Oxygen Atom in Trialkyl Phosphates (R,PO -R,P)/4. R. RC. RD . RF. Ethyl .............................................-0.370 - n-Propyl ....................................... 0450 0.430 0.375 n-Butyl .......................................... 0.493 0-435 0.433 A comparison of the properties of s.-and as.-ethyl sulphite (ethyl ethanesulphonate) is given below. P. RC. RD. RF. RG Mn2,o'. 0. s.-Ethyl sulphite ... . . .. . ..... . .. . . 297.6 31-76 31-91 32-27 32-54 195.44 as.-, , .................. 293.4 30.15 30.21 30.57 30.77 196.27 C Vogel and Cowaqa EXPERIMENTAL. Physical Meusurevnents.-The surface tensions and refractive indices were determined exactly as described in earlier papers (e.g. Part IIT J. 19!,8 1325). Four Pyrex surface-tension apparatus A B C and D were used the constants of which determined with AnalaR " sodium-dried benzene were 1.8725 2.3449 2.3740 and 2.4696 respectively.Except where another apparatus is specified apparatus A was used. In the determination of the densities the sample and all the apparatus (pycnometer and the small container for filling it with the sample) were kept in the thermostat at 20" f0.01" for at least 3 hours before the actual measurements; the room temperature was maintained as near 20" as possible. This procedure probably gave more trustworthy values of d:?O' than those obtained in the earlier measurements. For convenience of reference all the compounds studied in this and future communications will be numbered in Clarendon type. In the tabulated results t is the temperature h is the observed difference in height (in mm.) in the two arms of the U-tube H the corrected value d$ the density (calculated from the observed densities by assuming a linear variation with temperature) y the surface tension (dynes/cm.) computed from the equation y = KHd P the parachor and Mnz" the molecular refraction coefficient.The parachor was calculated in the usual way allowance for the density of the vapour (computed by Sugden's method J. 1925 127,1540) being made when the temperature of measurement was within 60" of the b. p. All the measurements of the refractive indices were carried out at 20" f0.02". Where 20" is used 20.0" is to be understood; nc nD nF nG are to be taken as referring to nF'Oo, etc. ; and Rc etc. to [R& etc. Unless otherwise stated all b. p.'s are corrected. Pvevious Work.-Parachor values the source of which is not indicated are taken from Sidgwick Sugden and Adam (Brit.Assoc. Re$. 1932 265). Reference is also made to what appears to be the most trustworthy of the earlier values of the refractive indices for comparison ; an exhaustive survey of all previous work would serve no useful purpose. Disulphides and Sulphides.-Most of the original measurements were made with samples supplied by Eastman Kodak. These were rigorously purified by chemical methods and by distillation until dzy and nge were constant. Some of the samples were prepared by us (sulphides from alkyl bromides and anhydrous sodium sulphide in alcoholic solution and disulphides by oxidation of a solution of the sodium thiol with iodine) ; excellent agreement was obtained in the physical properties of the synthetic and the purchased samples.In order to economise space the results of the measurements on the duplicate preparations will not be given. The disulphides were first distilled and the middle fraction was mechanically shaken with one-third of its volume of 5-10yo sodium hydroxide solution this treatment with alkali being repeated twice ; the products were then washed with distilled water until neutral dried with calcium chloride (shaking machine for 4 hour) kept overnight over fresh calcium chloride filtered and again dried by shaking with the same desiccant and distilled to constant a:!' and n?'. The sulphides were similarly purified except that 10-15~0 alkali solution was used and that for those thio-ethers which were distilled at atmospheric pressure the final distillation was made from sodium.Where distillation under diminished pressure was necessary the purified sulphide was first dried over calcium chloride then refluxed over sodium at 120" for at least 6 hours filtered and distilled under diminished pressure to constant di!' and ng". 1.Dimethyl disulphide (Eastman Kodak). B. p. 109-5"/774mm.; M 94-19; no 1-52167 nD 1.52599 nF 1.53690 nG. 1.54573; Rc 26.97 RD 27-15 RF 27.62 RG 28-00; RGr-c 1-03 Rp-c 0.65; Mnr 143.73. Densities determined : G? 1.0647 dt;.'' 1.0391 d:!'" 1.0162 d:?5" 0.9886. t. h. H. dfp"". Y. P. t. h. H. q0. Y. P. 14.1' 13.95 13.71 1.0715 34.87 213.6 62.3" 12-02 11.78 1.0157 28.40 214.1 41.0 12-89 12.65 1.0397 31.22 214.1 Mean 213.9 2. Diethyl disulphide.This was prepared by a modification of Kekul6 and Linnemann's method (AnnuZen 1862, 123 277). 77 G. of ethylthiol (Eastman Kodak b. p. 35"/768 mm.) were dissolved in 350 C.C. of 15% sodium hydroxide solution (calculated quantity for the formation of SEtNa) contained in a l-litre three-necked Pyrex flask fitted with a mechanical stirrer and a double-surface condenser. Stirring was continued until all the thiol had reacted ; the flask was cooled in ice. With constant stirring 135 g. of pure iodine were gradually added (2 hours) by momentarily removing the rubber bung from the third aperture of the flask and replacing it immediately the iodine had been added. After each addition the iodine gradually disappeared and an oily layer formed on the surface of the liquid. The mixture was stirred for a further 2.5 hours and kept for 2-5 hours.The colourless upper layer was separated and the aqueous layer extracted with ether; the combined liquids were washed with one-third the volume of 15% sodium hydroxide solution then twice with water and partly dried with calcium chloride and the ether removed. The resultant colourless liquid was shaken three times with one-third of its volume of 5% sodium hydroxide solution washed with water until free from alkali and dried with calcium chloride. The yield of crude product was 53.5 g. (70%) ; the main bulk boiled constantly at 152"/754 mm. ; a middle fraction was collected for the physical measurements. B. p. 152'1 754 mm.; M 122.24; nc 1-50329 nD 1.50704 nF 1.51653 no 1.52404; Rc 36.44 RD 36.67 RF 37-25 Ra 37.70; RG,* 1.26 RF-C0.81 ; MnEo 184.21.Densities determined d$" 0-9920 d;?'6D0.9702 d$"" 0.9534 d;!''" 0.9246. 17.3" 16.99 16.75 0.9946 31-19 290.5 61.4" 15.10 14.86 0.9527 26.51 291.1 41.1 16-06 15.81 0.9726 28.79 291.1 86.2 14.07 13.83 0.9288 24.06 291.5 Mean 291.1 (Baroni loc. cit. gives d:!' 0.9926 P 287.6 ; Bezzi Zoc. cit. gives b. p. 152-154"/760 mm. d:!' 0.9927 nE* 1.5070.) 3. Di-n-propyl disulphide (Eastman Kodak). B. p. 193.5"/750 mm. ; M 150.29; n,; 1.49465 nD 1.49813 nF1-50679 nG' 1.51359; Rc 45.63 RD 45-90 RF 46.58 RG 47.11 ; RG** 1.48 RF+ 0.95; Mng" 225.16. Densities determined d:Y 0.9599 d:!'20 0.9237 d:V' 0.9010. 18.8" 17-29 17.05 0.9609 30.68 368.1 87.3" 14-40 14-16 0.9004 23.87 369.0 61.8 15.43 15.19 0.9232 26.26 368.5 Mean 368.5 (Bezzi loc.cit. gives b. p. 191-192O/760 mm. d:? 0.9525 n2' 1.4981.) 4. Dzisopropyl disulphide. This was prepared as for diethyl disulphide except that the iodine was dissolved in 40% aqueous potassium iodide solution thus permitting the use of a dropping funnel. The quantities used were 24 g. of isopropylthiol (Eastman Kodak b. p. 50-51"/753 mm.) 12.6 g. of sodium hydroxide dissolved in 86 C.C. of water in a 500-C.C. three-necked flask and 38 g. (slight defect below theoretical quantity) of iodine in 100 C.C. of 40% aqueous potassium iodide solution. The yield of the crude product was 14 g. R. p. 176"/767 mm.; M 150.29; nc 1.48812 9tD 1.49164 92~1.50021 1.50687 ; Rc 45.90 RD46.18 RF 46.87 Rc,,47.40; Ra1-c 1.50 RF-~0.86; MnY 224-17. Densities determined d;!' 0.9435 d:!"" 0.9247 @' 6" 0.9085 d:!'4" 0-8853.[1943J Physical Properties and Chemical Coiastitutioilz. Part VII. Apparatus B. t. h. H. d$ . Y-P. t. h. H. d$. Y. P. 18.4" 13.15 12-91 0.9449 28.60 367.8 63.0" 11-59 11-35 0.9055 24.06 367.6 41.0 12.37 12-13 0.9245 26.30 368.1 86.4 10.94 10.70 0.8862 22.24 368.3 Mean 368.0 5. Di-n-butyl disulphide (Eastman Kodak). B. p. 230.5'1755 mm. 84'/3 mm. ; M 178.34; nc 1.48950 nD1.492!9 56.59; RG,+ 1.67 RF+ 1.07; Mn:" 266.19. Densities 9zF 1.50079 nG 1-50712; Rc 54.92 RD 55-21; Izp 55-99 RG~ determined d;!" 0.9383 dt!':400.9044 d;?" 0.8840. 15.5" 17.82 17.58 0.9419 31.01 446.8 86.3" 15.00 14.76 0.8837 24.42 448.3 61.4 15-96 18-72 0.9036 26.60 448.0 Mean 447.7 (Bezzi loc. cit. gives b.p. 143-144"/83 mm. d:!' 0.9306 1.49208.) 6. Diisobutyl disulphide. This was prepared and purified as described under 2. 43.5 G. of isobutylthiol (Eastman Iiodak b. p. 87.5"/764 mm.) 135 C.C. of 150/ sodium hydroxide solution and 52 g.of solid iodine yielded 37 g. of crude disulphide. B. p. 215"/767 mm. and 76.5"75 mm.; M 178.34; nc 1.48342 nD 1.48666 nF 1.49471 n8e 1-50102; Rc 54-94 RD 55-27 RF 56.04 RG' 56.66; RG~-c 1-71 RF+ 1.10; Mn?" 265.14. Densities determined d:!' 0-9275 d:i.4' 0.9090 d:!.6" 0.8922 d;?30 0.8718. 17.1' 16-49 16-25 0.9298 28.29 442.2 60.7" 14.80 14.56 0.8929 24.34 443.7 41.6 15.53 15.29 0-9088 26.02 443.2 86.2 13-87 13-63 0.8719 22-25 444.3 Mean 443.4 7. I,h-tert.-butyl disulphide. This was prepared from 30 g. of tert.-butylthiol (Eastman Kodak b.p. 63-64"/753 inm. dz? 0.7985 n2,0' 1.42246) 94 C.C. of 15% sodium hydroxide solution and 36 g. of iodine dissolved in 100 C.C.of 40% aqueous potassium iodide solution. The yield of pure product was 18 g. B. p. 64"/5.5 mm. (Rheinboldt hilott and Motzkus J. fw. Chenz. 1932 134,257 give b. p. 72'/11 mm.); M 178-34; nc 1.48664 nD 1.49003 %F 1.49844 9~~~~ 1.50501 ; Rc 55.54 RD 55.87 RF 56.68 Rat 57.31 ; RGt-c 1.77 RM 1.12 ; Mng" 265.73. Densities determined d:!' 0.9229 dj?.700.9039 d:?40 0.8906 dt!.3' 0.8713. 17.5" 16.02 15.78 0.9249 27.33 440.9 64.8" 14.14 13-90 0.8871 23.00 440.7 41.5 15.09 14.85 0.9057 25.18 441.1 87.9 13-29 13-05 0.8684 21.22 440.8 Mean 440.9 8. Di-n-amyl disulphide (Eastman Kodak). B. p. 119"/7 mm.; 111 206.40; nc 2.48549 TLD 1.48887 np 1.49673 1.50280; RC 64.21 RD 64-59 RF 65.47 RG,66-15; RG*-c1-94 RF-C1.26; Mnyn 307.32.Densities determined @" 0.9221 dt?*70 0.8906 di?"" 0.8708 di?0.7'0.8444. 18.5" 17.43 17.19 0.9233 29.72 522.0 87.1" 15.16 14.92 0.8708 24.33 526-4 61.0 15.96 15-72 0.8911 26.23 524.3 120.7 13.76 13.52 0.8444 21.38 525.6 Mean 524.6 9. Diisoanzyl disulphide (Eastman Kodak). B. p. 115'/9 mm.; M 206.40; nc 1.48320 nD 1.48637 nF 1.49423 91Ge 1.50035; Rc 64.15 RD 64-51 Rp 65.39 RG,66.09; R~n-c 1.94 RF-c 1-24; Mny 306.79. Densities determined d:!? 0.9192 di!.6' 0.8854 dtP 0.8655 di?1.500.8378. Apparatus C. 13.4" 13.49 13-26 0.9245 29.08 518.5 86.8' 11.41 11.17 0.8653 22.95 522.1 61.7 12.11 11.87 0.8852 24.94 521.1 120.2 10.48 10.24 0.8388 20.3'3 522.9 Mean 521.2 10.Methyl sulphide (Eastman Kodak).B. p. 37*8'/765 mm.; M 62.13; no 1.43272 ~zD1.43570 nF 1.44320 na' 1.44831; RC 19.02 RD 19.13 RF 19.41 RG,19.61; RG,% 0.59 RF-c 0.39; Mn?' 89.20. Densities determined d:? 0.8486 d:?oo 0-8456. A 12.9" 15.87 15.63 0.8529 24.96 163.0 C 14.6" 12.60 12.36 0.8619 25-00 163.3 B 17.3 12.60 12.36 0.8502 24.64 163.0 Mean 163.1 11.Methyl ethyl sulphide (Eastman Kodak). B. p. 66'1747 mm.; M 76.15; nc 143744 nD 144033 nF 1.44697 ??G 1-45306; Rc 23.62 RD23.75 RF 24.06 RG. 24-35; RGS-C0.73 RF-0.44; Mn2," 109.68. Densities determined 0.855i d:?" 0.8455 d$'.7" 0.8203. A 6.5" 16.84 16.60 0.8603 26.74 201.4 B 7.6" 13.41 13.17 0.8580 26.50 201-5 A 16.5 16.35 16.11 0.8494 25.62 201.8 B 22.3 12.85 12.61 0.8430 24.93 202.0 A 40.9 14.82 14.58 0.8201 22.39 202.3 B 41.3 11.79 11.55 0.8196 22.20 202.0 Mean 201.9 12.Ethyl sulphide.This was prepared by distilling an aqueous solution of sodium ethyl sulphate with excess of sodium sulphide until the temperature of the reaction mixture was 120'. The sulphide layer in the aqueous distillate was removed shaken several times with 20% sodium hydroxide solution then kept over sodium hydroxide pellets for 24 hours washed with water until neutral dried with calcium chloride and distilled over sodium. B. p. 92'1761 mm. ; A1 90.18; nc 1.43987 nD 1-44235 nF 1.44979 no' 1.45523 ; Rc 28.39 RD 28.53 RF 28-95 RG. 29.25; RG'+ 0.86 RF-c0.56 ; Mnr 130.08. Densities determined d:!? 0.8369 d44?.400.8155 d:p5' 0.7961. 13.5" 16.61 16-37 0.8434 25.85 241.1 61.5' 14.04 13-80 0.7950 20.54 241.9 41.3 15.14 14.90 0.8156 22.75 241.5 Mean 241.5 (Baroni 106.cit. gives 0.8367 ys0. 22-19 P 239.1 ; Bezzi loc. cit. gives b. p. 93-94'/760 mm. d:,O' 0.8278 ?z? 1-44303.) Vogel and Cowan 13. n-Propyl sulphide (Eastman Kodak). B. p. 142"/762 mm.; M 118.23; nc 1.44622 ?t~ 1.44896 %p 1.45567 no# 1.46077; RO37.59 RD37.79 Rp 38.28 RoO 38.64; RG'+ 1-05 RF~ G?'0.8391 d46?*'* 0.8013 d:Y* 0.7804. 0.69; Mn2,0" 171.30. Densities determined t. h. H. a:-. Y* P. t. h. H. d$. Y. P. 16.4" 17.19 16.95 0.8423 26.72 319-1 86.7' 13.60 13.36 0.7791 19.49 318-8 61.9 14.77 14.53 0.8013 21-80 318.8 Mean 318.9 (Mann and Purdie J. 1935 1549 give b. p. 139" dap' 0.84315 Bezzi loc. cit. gives b. p. 140-143"/760 mm., e?0.8302 nZn1.44904.) 14.isoPro+yZ sutphide. This was prepared by adding 181 g. of isopropyl bromide b. p. 59-59.5'/765 mm. slowly to a boiling mixture of 224 g. of finely-powdered anhydrous sodium sulphide and excess of rectified spirit the whole refluxed for 7 hours and the alcohol distilled off (compare Winssinger BUZZ. Soc. chim. 1887 48 109;. Mann and Purdie Zoc. cit.). The distillate was diluted with excess of water and the crude sulphide (70 g.) purified in the usual manner with 10% sodium hydroxide solution etc. B. p. 119"/761 mm. ; M 118.23; no 1.43628 nD 1.43950 nF 1.44574 na,1.45093; Ro 37-88 RD 38.12 RP 38.59 RQ' 38.98; Rot+ 1.10 RF-C0.71; Mny 170.19. Densities determined 0.8166 d44!.4' 0.7960 d:?"' 0.7775 dq!"' 0.7534. Apparatus B. 9.5" 12-78 12.54 0.8266 24.31 317.6 60.6' 10.76 10.52 0.7781 19-19 318.2 42.3 11.42 11.18 0.7951 20.84 317.7 86.2 9.75 9.51 0.7545 16.83 318.1 Mean 317.9 (Mann and Purdie Zoc.cit. give b. p. 120O.) 15. n-ButyZ sulfihide (Eastman Kodak). B. p. 187'/765 mm.; M 146.28; no 1.45031 ?ZD1.46297 %F 1.45954 1.46458; RO 46.82 RD 47.06 Rp 47.64 Rae 48.10; Ra-o 1.28 RM 0.82; Mna,o' 212.54. Densities determined 0.8402 d,6'.2' 0.8040 d:?." 0.7843. Apparatus B. 18.3" 14.12 13.88 0.8417 27.40 397.6 87.8" 11.65 11.41 0.7828 20.94 400.0 61.7 12.66 12.42 0.8036 23.40 400.4 Mean 399-3 (Mann and Purdie Zoc. cit. give b. p. 185-185*5' d240 0.8352 ~24.26.45 P 395.5; Bezzi loc. cit. gives b. p. 182-184"/760 mm. d:? 0.8334 nzo 1.45405.) 16. isoButyl sulphide (Eastman Kodak). B. p.169'1772 mm.; M 146-28; no 1.44420 nn 1.44686 np 1-45353 ?to. 1.45823; Rc 47.04 RD 47.29 RR~ 47-90 Ran 48.32; Ra*+ 1.28 RM 0.86; Mny 211.65. Densities determined : dzr 0.8263 dii.2*0.8106 d:F7' 0.7918 d:?.6' 0,7712. 14.7' 16.60 16.36 0.8306 25.44 395.5 62.3" 14.38 14.14 0.7922 20.98 395.2 41.1 15-39 15.15 0.8107 23.00 395.1 88.2 13.32 13.08 0.7706 18.87 395.7 Mean 395.4 (Mann and Purdie Zoc. cit. give b. p. 174" d" 0.8301 ~24.24.90 P 392.8.) 17. sec.-Butyl sulphide. This was prepared from 68.5 g. of sec.-butyl bromide b. p. 90.5-92"/756 mm. 58.5 g. of finely-powdered anhydrous sodium sulphide and 200 C.C. of boiling rectified spirit as detailed under 14. The yield of crude thio-ether was 26 g. B. p. 164-5"/739 mm.; M 146.28; no 1.44793 nD 1-45062 np 1.45715 no#1.46220; Rc 46.90 RD 47.14 Rp 47.74 Ral 48.19; Rc.-o 1.29 R-0.84; Mny 212.19.Densities determined d:? 0.8348 dii.300.8163 d:?*3" 0.7996 d,S.B*O0 0.7800. Apparatus C. 12.0' 13.53 13.29 0.8416 26.55 394.6 62.0" 11.76 11.52 0.7990 21-85 395.7 25.2 13.12 12.88 0.8304 25.39 395.4 85.6 10.76 10.52 0.7795 19.47 394-2 40-8 12.46 12-22 0-8167 23.69 395.2 Mean 395.0 tert.-Butyl sulphide. All attempts to prepare this compound from tert.-butyl bromide b. p. 72.5-73-5"/766 mm. and anhydrous sodium sulphide in alcoholic solution were unsuccessful. 18. n-Amyl sulphide (Eastman Kodak). B. p. 84.5'14 mm.; M 174.34; no 1.45352 nD 1.45617 nF 1.46262 nG. 1.46750; Ro 56.09 RD 56.38 Rp 57.06 RQ~ 57-58; RG*+ 1.49 RM 0.97; Mny 253.87. Densities determined d:O' 0.8409 d46?.70 0.8091 d,S!.700.7904.17.3" 18-01 17.77 0.8429 28-05 476.0 86.9' 15.11 14.97 0.7895 21.98 478.1 62.2 16.10 15.86 0.8095 24.04 476.9 Mean 477-0 (Mann and Purdie Zoc. cit. give b. p. 108-109"/15 mm. d" 04408 ~24027-60 P 474.8.) 19. isoAmyl sulphide (Eastman Kodak). B. p. 85.5'/5 mm.; M 174.34; no 1.45002 nD 1-45267 nF 1.45912 na 1.46403; Rc 56.18 RD 56.47 RF 57-16 R,y 57.68; Rat-1-50 Rpc 0.98; Mny 253.26. Densities determined dip 0.8340 dz! 0' 0.8031 d$.6* 0.7830 d:?0'30 0.7567. Apparatus B. 15.2" 13.71 13.47 0.8377 26.46 472.0 87.4" 11.37 11.13 0.7823 20.42 473.7 62.0 12.14 11.90 0.8016 22.37 473.0 121.8 10.20 9.96 0.7555 17.64 473.0 Mean 472.9 20. n-HexyZ sulphide. This was prepared from 69 g. of n-hexyl bromide b.p. 154-5-156"/759 mm.[from n-hexyl alcohol b. p. 156-157"/765 mm. (Carbide and Carbon Chemicals Corporation) by hydrogen bromide-sulphuric acid method] 49 g. of anhydrous sodium sulphide and 88 C.C. of rectified spirit and refluxing for 20 hours on the steam- bath (compare 14). The yield of crude product was 38 g. B. p. 113-5"/4 mm. ; M 202.39; nc 1.45596 nD 1.45856 nF 1.46492 no-1.46965. Rc 66-41 RD65.73 RF 66.51 Ra* 67-10; RQ*-c1.69 RM 1-10; Mng 295.21. Densities determined di.0' 0.8411; dj?'Oe 0.8264 dq6?*' 0.8140 dz:'70 0.7941. [19431 Physical Properties and Chemical Constitutioia. Part VII. Apparatus D. 1. h. H. d;. . Y. P. t. h. H. q0. Y. P. 25.3" 13-78 13.54 0-8373 28.00 556.0 62.3" 12.64 12.40 0.8113 24.84 556.9 28.9 13-65 13.41 0.8348 27-65 555.9 88.7 11.82 11.58 0.7921 22.65 557.4 41.9 13.85 13.01 0.8258 26-53 556.2 Mean 556-5 (Mann and Purdie Zoc.cit. give b. p. 136-138"/20 mm. da4' 0.8447 ~24.27.83 P 549-2.) 21. n-HeptyZ suZphide. This was prepared from 60 g. of n-heptyl bromide b. p. 178-179"/762 mm. (from n-heptyl alcohol b. p. 175.5-176-5"/771 mm. ; " Organic Syntheses," 1926 6 52 by hydrogen bromide-sulphuric acid method) 39 g. of anhydrous sodium sulphide 70 C.C. of rectified spirit and refluxing on the steam-bath for 20 hours. The yield of the crude dry product was 35.5 g. B. p. 141.5"/4-5 mm.; M 230.44; nc 1.45799 nD 1-46055 nF 1.46687 NG' 1.47137; Ra 74-72 RD 75.09 RF 75.96 RGl 76.59; 1.87 RF-C1.24; Mn:* 336.58. Densities determined 49' 0.8416 di!!'6' 0.8277 d:P6' 0.8147 d:?" 0.7968.20.2" 18.82 18-58 0.8414 29.27 637.0 60-7" 17.30 17.06 0.8146 26.02 638.8 41.4 18.03 17.81 0.8278 27.61 638.1 87.7 16-21 15.97 0.7961 23.81 639.4 Mean 638.4 (Mann and Purdie Zoc. cit. give b. p. 164"/20 mm. da' 0.8402 7210 28.61 P 633.6.) 22. n-OctyZ sulphide. This was prepared from 64 g. of n-octyl bromide b.p. 200-200-5"/764 mm. (from n-octyl alcohol b. p. 193-194"/763-5 mm. Deutsche Hydrierwerke Akt. by the same method as 21),39 g. of anhydrous sodium sulphide 70 C.C. of rectified spirit and refluxing for 20 hours on the steam-bath. The yield of the crude dry product was 39-5 g. B. p. 161-5"/4 mm.; M 258.49; no 1.45958 nD 1-46215 nF 1.46848 NG' 1.47310; Ro 83.75 RD 84.16 Rp 85-14 Ran 85-86; RG0-0 2-11 RFW1-39; Mnzo377.96. Densities determined 4P.O'whence d;?' 0.8447 (extrap.), di;"' 0.8295 d$"O' 0-8164 da?*4' 0-7977.Apparatus D. 21.7 14.78 14.54 0.8434 30-28 719.0 61.1" 13.27 13.03 0.8156 26-25 717.3 25.9 14-66 14.41 0.8405 29-91 719.2 87.4 12.50 12.26 0.7977 24.15 718.4 41.3 13.82 13-55 0-8293 27.81 716.0 Mean 718-0 (Mann and Purdie Zoc. cit. give b. p. 184-186"/20 mm. da4' 0-8409 y"' 29.10 P 713.5.) 23. Methyl n-butyl sulphide. 23.5 G. of n-butylthiol b. p. 98-98.5"/766 mm. (Eastman Kodak redistilled) were dropped slowly into 205 C.C. of 10% aqueous sodium hydroxide solution with vigorous stirring which was continued until the liquid was homogeneous. 32.2 G. of methyl sulphate were added during 1 hour. The liquid soon became cloudy and heat was evolved. Stirring was continued for 2 hours at room temperature and the mixture set aside for 6 hours.The upper layer of sulphide was then removed washed 4 times with one-quarter of its volume of 10% sodium hydroxide solution then with water until neutral and dried with calcium chloride. The yield of the crude dry product was 22.5 g. It was distilled from sodium in a fractionating Claisen flask and a middle fraction collected. B. p. 122.5'1 761 mm.; M 104.21 no 1.44498 nD 1.44776 np 1.45452 1.45974; Ra 32-92 RD 33.10 RF 33-53 Rat 33.94; RGP-O 1.02 ; RF-C0.61 ; Mny 150.93. Densities determined :G!*043427 d $?;" 0-8239 d'$?' 0.8055 d!?lo 0.7809. 21.0" 16.83 16-59 0.8418 26-15 280.1 61-6" 14.74 14-50 0.8046 21.85 280.1 42.1 15-77 15.53 0.8226 23.92 280.3 91.3 13.19 12.95 0.7770 18.84 280.0 Mean 280.1 24.Methyl isohtyl sulphide. This was prepared from 24.3 g. of isobutylthiol (Eastman Kodak b. p. 87*5"/764 mm.) 210 C.C. of 10% sodium hydroxide solution and 33.2 g. of methyl sulphate as under 23. The yield of crude product was 24 g. B. p. 112.5"/760 mm. ; M 104.21 ; nc 1.44062 nD 1.44333 ; nF 1.45004. nG1 1.45515; Ro 32.99 RD 33.17 RF 33-60,. Rap 33.93; Ras-0.94 RF-C0.61; Mny 150.41. Densities determined 4:. 0.8335 d44?'4' 0.8146 d:."2" 0.7971 df!'2' 0,7757. 20.7" 16.22 15.98 0.8329 24.92 279-6 63.3" 14.17 13.93 0-7953 20.74 279.6 43.4 15.20 14.96 0.8136 22.79 279.9 88.1 12.80 12.56 0.7723 18.16 279.1 Mean 279.6 25. Methyl tert.-butyl sulphide. This was prepared from 23 g. of tert.-butylthiol (Eastman Kodak redistilled) b. p. 63-64",'753 mm.200 C.C. of 10% sodium hydroxide solution and 31.5 g. of methyl sulphate as under 23. The yield of crude product was 19.5 g. B. p. 99"/766 mm. (Rheinboldt Mott and Motzkus Zoc. cit. give b. p. 101-102°); M 104.21 ; 1%~1143743 nu 1.44023 nF 1-44703 nGg.1.45229; Rc- 33.10 RD 33-29 RF 33-73 Rap 34.08 ; RG*-c0.98; RF-c 0.63 ; Mng 150.14. Densities determined e$'0-8257 d4PF9 0.8060 ds!'5 0.7836. 19.0" 15.48 15.24 0.8266 23.59 277.9 62.8" 13.20 12.96 0.7852 19.05 278.0 41.4 14.34 14.10 0-8055 21-27 277.9 Mean 277.9 26. Ethyl n-butyl sulphide (Eastman Kodak). B. p. 1426"/758 mm. ; ill 118.23 ; no 1.44604 nD 1.44876 'PZF 1,45549 nG1 1.46069; Rc 37.68 RD 37.89 Rp 38.38 RGe 38-75; 1.09 R~c 0.70; Mn2,o' 171.29. Densities determined @!' 0.8367 dif'4' 0.8200 d!?'3' 0-8034.Apparatus D. 1S.O" 13.10 12.86 0.8377 26-60 320.5 41-1" 12-23 11.99 0.8202 24.29 320.0 23.5 12.93 12.69 0.8339 26.13 320.5 60.9 11-52 11.28 0.8029 22.37 320.2 Mean 320.3 27. Ethyl tert.-butyl sulphide. This was prepared from 17.7 g. of tert.-butylthiol 200 C.C. of 10% sodium hydroxide solution and 30.3 g. of ethyl sulphate as under 23. The yield of crude product was 15 g. B. p. 119.5"/761 mm. (Rheinboldt Mott and Motzkus Zoc. cit. give b. p. 56-57"/109 mm.) ; M 118.23 ; nc 1.43890 nD 1.44164 nF 1.44844 RaO no' 1.45356; Rc 37-93 RD 38-12 RF 38.63 39-02; RG,* 1.09 RFC 0-70; Mn$" 170.44. Densities determined 0.8200 d44!'3' 0.8021 d!?"' 0.7848 d:V O~i615. 21.5" 15-45 15.24 0.8187 23.36 317.5 59.6" 13-66 13.42 0.7859 19.i.5 317.1 43.6) 14.52 14.28 0.8006 21-11 317-7 87.5 12.23 11.99 0.7608 17.08 316.6 Mean 317.2 Vogel and Cowa9g 28.Phenyl sulphide. This was prepared from redistilled sulphur monochloride b. p. 133-134"/750 mm. and sodium-dried " AnalaR " benzene by the Friedel-Crafts reaction (" Organic Syntheses," 1934 14 36) ; a perfectly-colourless and constant-boiling product was obtained. B. p. 145"/8 mm. ; M 186-26 ; nc 1.62575 nu 1-63343,+ZF 1.65375 HG 1-67158; RC 59.19 Rn 59-77 RF 61.29 RG,62.60; 3.41 RF-c 2-10; Mng' 301.24. Densities determined d'?' 1.1136 dt! lo 1.0823 di!'8" 1.0628 d;?' 1.0352. Apparatus B. t. h. H. d$ . Y. P. 2. h. H. (?yo. Y* P. 16.4" 16.49 16.25 1.1164 42-54 426.1 86.4" 14.64 14.40 1.0616 35.85 429.3 61.9 15.27 15.03 1.0809 38.10 428.1 121.6 13-44 13.20 1.0346 32.02 128.3 Mean 428.0 29.Phenyl selenide. This was obtained as a reddish-yellow liquid as described in " Organic Syntheses," 1938 18 27. B. p. 141°/4 mm.; M 233.16; nD 1.65002*; RD 62.93; Mny 384-71. Densities determined d;!' 1.3525 d:? So 1.3174 d:?'" 1.2902 d;?"" 1.2628. ,4pparatus B. 23.5" 13.86 13.62 1.3484 43-07 443.0 88.5" 12-35 12.11 1.2904 36.64 444.6 61.0 13.17 12-93 1.3152 39.88 445-5 121.3 11.50 11-26 1.2623 33.33 443.8 Mean 144.2 Alkyl Su1phites.-The general method of preparation consisted in placing redistilled thionyl chloride (0.5 mol.) in a 100-c.c. Claisen flask cooling it in ice and adding the pure alcohol (0.75 mol.) from a tap-funnel during about 1 hour. Hydrogen chloride was rapidly evolved and it was necessary to shake the flask vigorously and frequently in order to ensure complete interaction.The mixture was refluxed for 45-75 mins. in order to complete the reaction and then distilled. n-Butyl n-amyl and isoamyl sulphites were distilled under diminished pressure. t The crude sulphite was thoroughly dried with anhydrous sodium sulphate redistilled and a middle fraction collected for the physical measurements. The latter were made on the same day as the final distillation for the sulphites slowly decompose on keeping. The yields were excellent. The alcohols employed were A.R. absolute methyl and ethyl alcohol (Burrough) n-propyl alcohol b. p. 96-97"/ 760 mm. (Bisol) isopropyl alcohol b. p. 82-83"/751 mm. (Bisol) n-butyl alcohol b. p. 116-117"/762 mm. (Bisol), isobutyl alcohol b.p. 106~5-107-5"/766 mm. (Bisol) n-amyl alcohol b. p. 136-6-137-5"/765 mm. (Sharples) and zsoamyl alcohol b. p. 129-130"/765 mm. (Sharples synthetic). All the alcohols were dried over A.R. potassium carbonate before fractionation. 30. Methyl sulphite. B. p. 126'1760 mm. ; M 110.13; nc 1.40712 nD 1.40929 nF 1.41464 not 1.4181'7; Rc 22.36 22.90; R~j-00.54 0.36; Mn2,0' 155.21. Densities determined dq'? 1-2129 d:!"" 1.1.%7, RD 22.46 RF 22.72 RG~ d:!'3" 1.1256. Apparatus C. 17.8" 12.10 11.86 1.2158 34.23 219-1 87-6" 9.77 9.53 1.1252 25.46 219.1 61.9 10.71 10.47 1.1587 28.80 220-0 Mean 219.i 31. Ethyl sulphite. B. p. 157"/763 mm.; M 138.18; nc 1.41223 nD 1.41441 nF 1.41974 na' 1.42367; Rc 31.76 32.54; 0.78 RF* 0.51 ; Mnr 195.44. Densities determined d;!* 1.0829 d:!"" 1.0604, RD 31.91 RB 32.27 RG~ dtt O0 1.0396 d:! 3" 1.0125.Apparatus D. 22.9" 11.21 10.97 1.0798 29.25 297.6 61-0" 10.05 9-82 1.0396 25.19 297.8 29.0 11.03 10.79 1-0733 28.60 297.7 85.9 9.25 9.01 1.0119 22.52 297-5 43.1 10.56 10.32 1.0583 26-97 297.6 Mean 297.6 32. n-Propyl sulphite. B. p. 191"/764 mm. (uncorr.) ; M 166.23; nc 1.42200 nn 1-42426 np 1.42969 1.43368; Rc 41.09 RD41-29 RF 41.75 RG 42.08; R~1-c 0.99 Rpa 0.66; MnEo 236.76. Densities determined di? 1.0280 d!?'700.9880 d;P5' 0.9642 di?"30 0.9269. 18.9" 15.22 14-98 1.0291 28.87 374.4 86.2" 12-72 12.48 0.9635 22.52 375.8 61.9 13.60 13.36 0.9878 24.71 375.2 121.3 11.39 11.15 0.9269 19.35 376.2 Mean 375.4 33. isoPropy1 sulphite. B. p. 169-5"/764 (uncorr.) ; M 166.23; no 1-41255 nD 1.41476 nF 1.42009 1.1~' 1.42399; Rc 41.15 RD 41.35 Rp 41.81 RG 42.15; Ra,-c 1-00 RF+ 0.66; Mny" 235.18.Densities determined d:!' 1.0064 dz?'3' 0.9644 die.'- 0.9387 d:?' 0.9016. 18.6" 14.21 13.97 1-0078 26.36 373.8 87.4' 11.63 11.39 0.9383 20.01 374.7 61.5 12.57 12.33 0.9652 22-28 374.2 120.8 10.42 10.18 0.9015 17.18 375.4 Mean 374.5 34. n-Butyl sulphzite. B. p. 90-5"/5 mm.; M 194.28; no 1.42864 nD 1.43098 np 1.43638 nd' 1.44036; Rc 50.26, RD 50.51 RF 51-06' RG,51.47; Ra,+ 1-21 RF-0.80;Mnr 275-47. Densities determined d:? 0-9957 d44t.l" 0.9775 d!! 0.9603 d:8 ''0.9381. Apparatus D. 19.0" 11.99 11.75 0.9966 28-92 452.1 42-2" 11.32 11.08 0-9765 26.72 452.5 22.4 11-89 11.65 0.9940 28.60 452.0 62.4 10.78 10.54 0.9589 24.96 352.9 30-5 11.71 11.47 0.9866 27-95 451.7 86.0 10-14 9.90 0.9378 22-93 453.8 Mean 452.5 35.isoButyl sulphite. B. p. 209"/741 mm. ; M 194-28; no 1.42451 nD 1.42676 nF 1.43223 nap 1.43631 ; Rc 50.32 0.80; Mnp 277-20. Densities determined d:!' 0.9862 dt!'7' 0.9484, RD50.56 RF 51-12 RG 51-54; RG~-c1.22 R~c d$'5" 0.9225 di.21*7' 0.8897. * C line almost coincident with D ; F and G' lines not visible. t Compare " Organic Syntheses," 1939 19,29 for n-butyl sulphite ; these details were published after the authors' work was completed in 1937-38. [19431 Physical Proparties and Chemical Comtitzztiow Part VII. t. h . H. d$ . Y. P. t. h. H. d$. Y. P. 15.2" 15.11 14.87 0.9905 27.58 449.5 87.9" 12.43 12-19 0.9221 21.05 451.3 62.0 13.39 13-15 0.9481 23.35 450.4 122.4 11.17 10.93 0.8891 18.20 451.3 Mean 450.6 36.n-,4nzyl sulphite. B. p. 111.5"/5 mm.; M 222.34; no 1.43393 nD 1.43620 nF 1.44178 nG 1.44584; Rc 59.52 60.94; RG~+1.42 RF-c 0.96; Mng" 319.33. Densities determined d:? 0.9726 d:JS5"0,9385, RD59.80 RF 60-48 RG~ d:?" 0.9160 da?0'300.8878. 16.0" 16.26 16.02 0.9758 -29.27 530.0 87.5" 13.72 13.48 0.9164 23.10 531.9 61.7 14.75 14-51 0.9383 25.49 532.5 122.3 12.56 12.31 0.8862 20.43 533.4 Mean 532.0 37. isoAnzy1 sulphite. B. p. 98.5','4 mm. ; M 222.34; nc 1.43318 n~ 1.43550 nF 1.44104 na 81.44521 ; Rc 59.44 RD 59.71 RF 60.37 RG,60.86; 1.42 R-0.93; Mn?" 319.15. Densities determined d:?' 0.9726 da9.g00.9552 d2!.500.9381 d 0t?'2"-9181. 15.5" 15.71 15.47 0.9763 28.28 525.2 62.7" 13.97 13.73 0.9371 24-09 525.6 41-4 14.79 14-55 0-9548 26.01 525.9 87.0 13.14 12-90 0.9166 22-14 526.2 Mean 525.7 38.Ethyl ethanesulphonate (as.-ethyl sulphite) . Pure silver sulphite (from Johnson and Matthey's silver nitrate pure recrystallised) was refluxed with colourless ethyl iodide in dry ethereal solution (Biltz and Biltz " Laboratory Methods of Inorganic Chemistry," 1928 211 ; Kurbatow Annalen 1874 178 7) ; the resultant ester (poor yield) was purified by repeated fractionation. B. p. 210"/760 mm.; M 138.18; nc 1.41842 nD 1.42036 nF 1.42496 PZG~1.42819; Rc 30.15 HD 30.21 RF 30.57 RGt 30.77; RG.+ 0.62 RF-C0.42; Mng' 196-27. Densities determined d;!' 1-1560 d:Z'Oo 1.1356 di?6' 1.1150 d::"" 1.0906. 19.3" 16.84 16.60 1-1567 35.96 292.5 62.0" 15.43 15.19 1.1155 31.73 294.0 30.1 16.53 16.29 1-1463 34.97 293.0 86.2 14.52 14-28 1.0914 29.18 294.3 41.9 16.14 15.90 1.1357 33.81 293.4 Mean 293.4 (Sugden et al.give P 295.8.) Alkyl Su1phates.-Commercial methyl sulphate (B.D.H. 100 8.) was kept over " AnalaR " potassium carbonate for 36 hours and then twice distilled. Ethyl sulphate (B.D.H.) n-propyl and n-butyl sulphates (Eastman Kodak) were purified as follows. 50 G. were shaken for 10 mins. with 15 C.C. of saturated sodium carbonate solution the ester layer separated shaken mechanically for 30 mins. with calcium chloride filtered and kept over a large quantity y! calcium chloride for 24 hours with occasional shaking. The ester was again filtered into a large excess of AnalaR potassium carbonate kept for 24 hours and distilled (compare Barkenbus and Owen J.Amer. Chem. SOC.,1934 56, 1024). 39. Methyl sulphate. B. p. 187.5"/763 mm.; M 126.13; nc 1-38574,nD 1.38740 nF 1-39123,no. 1.39389; Rc 22-29 22.71 ; RG+c0.42 RFc 0-28; M$* n175-00. Densities determined d:Y 1.3283 di.3''' 1.3003, RD 22-38 RF22-57 RG~ di?'8e 1.2777 d:B"* 1-2478. 15.1' 16.05 15.81 1.3342 39.50 237.0 61.4" 14.44 14.20 1.2782 33.99 238.3 40.6 15.23 14.99 1.3043 36.61 237.3 86.5 13-61 13-37 1.2482 31-25 238.9 Mean 237.9 (Sugden Reed and Wilkins J. 1925 127 1539 give b. p. 187.5"/769 mm. P 238.9; the value for d$" extrapolated from their results is 1.3322.) 40. Ethyl sulphate. B. p. 75'15 mm.; M 154.18; no 1.39861 nD 1.40037 nF 1.40457 n~, 1.40756; RC 31-65 RD31-77 RF 32.07 RG'32.28; RG'-c0-63 RF-c 0.42; Mnr 215.81.Densities determined d:3" 1.1774 d:?'7' 1,1350 d:B'4 1.1095 d:?0'9" 1.0719. Apparatus C. 14.9" 12.36 12.12 1.1825 34.02 314.9 86.4" 10-48 10.24 1-1095 26.97 316.7 61.9 11.18 10.04 1.1348 29-47 316.6 120.7 9.56 9.32 1.0721 23.72 317.4 Mean 316.4 [Sugden Reed and Wilkins loc. cit. give b. p. 110"/30 mm. P 313.8 d:?" (extrap.) 1-188; Buehler Gardner and Clemens J. Org. Chem. 1927 2 170 give b. p. 77-8-78.0"/6 mm. P 318-4.1 41. n-Propyl sulphate. B. p. 94'15 mm.; M 182.23; nc 1.41144 nD 1-41336 nF 1.41788 na#1.42104; Rc 40.79 0.83 IZF-0.56; Mng' 257.56. Densities determined @y 1.1102 d!8'20 1.0683, RD 40.96 RF 41.35 RG*41-62; RGP-C d,8!'7" 1.0452 d:39"0 1 e013.5. 13.3" 15.89 15-65 1.1167 32.73 390.3 87.0" 13.41 13-17 1.0459 25-79 392.6 61.7 14.26 14.02 1.0695 28.08 392.2 120.1 12.32 12.08 1.0133 22.92 393.4 Mean 392.2 42.n-Butyl sulphate. B. p. 109-5"/4 mm.; M 210.28; nc 1-41929 nD 1.42126 nF 1-42597 ng 1.429361 RC50.05 RD50.26 RF50.74 RG,51-11; RGS-C1.06 RFC 0.69; Mngo 298-87. Densities determined @? 1.0616 d::." 1.0227 dz!'90 1.0039 d:!9"' 0.9727. 13.6" 16.14 15.90 1.0673 31.77 467.9 85.5" 13-80 13.56 1.0043 25.50 470.5 62.3 14.49 14.25 1.0214 27.25 470.4 120.6 12.54 12.30 0.9717 22.38 470.7 Mean 469.9 Trialkyl 0rthophosphates.-These were prepared by the action of redistilled phosphorus oxychloride upon the sodium alkoxides as described by Evans Davies and Jones (J. 1930 1310) and were purified by at least two distillations under diminished pressure. The b.p.'s of the alcohols employed are those given under Alkyl Sulphtites. The agreement of the authors' measurements of the densities and refractive indices with those of Evans Davies and Jones (loc. cit.) is moderate Physical Profierties and Chemical ConstitutioPz. Part VII. 43. Trimethyl orthophosphate. B. p. 62"/5 mm.; M 140.08; no 1.39452 nD 1.39630 %F 1.40049 na' 1.40154; Ra 27.67 RD 27.74 RF 27.99 Ra4 28.06; Rae+ 0.39 Rp-0 0-32; Mny 195.59. Densities determined @ 1.2144 d:?'" 1.1722 d$?7' 1.1436 d:.'g.9' 1.1062. f. h. 3.. d$ . Y. P. t. h. H. dTe. Y. P. 17.5" 16.86 16-62 1.2152 37.76 285-9 86.9" 14-17 13-93 1.1432 29.82 286.3 60.9 15.22 14-98 1,1722 32.88 286.2 120.7 12.83 12.59 1.1053 26.06 286.3 Mean 286.2 [Evans Davies and Jones Zoc.cit. give b. p. 73"/10 mm. dye 1.2052 Gr 1.2104 (extrap.) nt5' 1.3934 n2,6' 1-3950 nZ5O 1.3990; RC27.769 RD27.869 Rp 28.119.1 44. Triethyl orthophosphate. B p. 75.5"/5 mm.; M 182.16; no 1-40343 nD 1.40533 nF 1.40983 nan 1.41308; Rc 41.60 121 41.77 RF 42.18 RG*42-48; RG,~: 0-88;RF0 0.58; Mn2,0' 255.19. Densities determined @ 1.0695 d460"' 1.0301 d2Y' 1.0021 di?O'l' 0.9708. Apparatus B. 18.3" 12.27 12.03 1.0712 30.22 398.7 87.4" 10.26 10.02 1.0014 23.53 400.6 61.7 11-01 10-77 1.0293 25.99 399.6 121.1 9.35 9-11 0.9698 20.72 400.7 Mean 399.9 [Sugden Reed and Wilkins Zoc. cit. give b. p. 108"/25 mm. d;!' 1.0737 (extrap.) P 399.1 ; Evans Davies and Jones loc. cit. give b. p. 90"/10 mm. d::' 1.0637 d22* 1-0685 (extrap.) ntg' 1.4021 n2,6' 1.4039 ng?* 1-4082; Rc 41.706 RD 41.870 Rp 42.263.1 45.Tri-n-propyl orthophosphate. B. p. 107.5"/5 mm.; M 224.24; nc 1.4148 nD 1.41646 nB 1.42120 NG' 1.42467; Ro 55.42 RD 55.66 RF 56.21 Ran 56-62; Ran+ 1.20 R-0.79; Mng' 317.63. Densities determined @!* 1.0121, d:?'" 0-9743 d:l"" 0.9518 di?0'7' 0.9209. 16.9" 15.78 15.54 1.0149 29.46 516.0 87.6' 13.17 12.93 0.9513 23.04 516.4 63.0 13-98 13-74 0.9735 25-05 515.3 121.8 11-88 11-64 0.9199 20.05 515.8 Mean 515.9 [Evans Davies and Jones Zoc. cit. give b. p. 121°/10 mrn. e?1-0023 4:. 1.0071 (extrap.) ng' 1.4118 n2,6' 1.4136 t~f 1.4182 ; Ro 55.635 RD 55.849 RF 56-394.1 46. Triisopropyl orthoflhosphate. B. p. 83.5"/5 mm.; M 224.24; no 1.40376 nD 1.40573 np 1.41034 na' 1-41366; Ro 55.56 RD55-79 Rg 56.34 Ro. 56-76; Rae4 1.20 RF-CJ0.88; Mn2,0* 315.21.Densities determined G?0.9867 dz?i6' 0.9472 d:?;" 0.9237 d:!"" 0.8931. 15.3' 14-08 13.84 0.9909 25.68 509.4 87.1' 11-50 11.26 0.9241 19.48 509.8 61.7 12.36 12.12 0.9478 21.51 509.5 120.4 10.45 10.21 0.8926 17-06 510.6 Mean 509.9 47. Tri-n-butyl orthophosphate. B. p. 138.5"/6 mm.; M 266.32 no 142295 nD 1.42496 %F 1.42988 nas 1.43343; Rc F9.44 RD69.57 RF 70-43 Rae 70.93; Rae-1.49 Rp-c 0.99; Mnr 379.50. Densities determined fl 0.9766 d:F3 0.9431 d;!'" 0.9226 d:F0 0.8941. 16.6" 15-59 15.35 0.9794 28.15 626.3 87.3" 13.20 12.96 0.9224 22-38 628-0 62.1 14.39 14.15 0.9433 24.99 631.3 121.6 12.24 12.00 0.8932 20.07 631.1 Mean 629.2 [Evans Davies and Jones Zoc. cit. give b. p. lSO"/lO mm. dip' 0.9727,a:!, 0-9774 (extrap.) ni6* 1.4203 nr 1-4224, ng5' 1.4274; RC 69.312 RD 69.616 RF 70.336.They state that it is slightly yellowish the colour indicating incipient decomposition." Our specimen was perfectly colourless and its properties did not change on distillation under diminished pressure.] 48. TriisobutyZ orthophosphate. B. p. 117"/5.5 mm.; M 266.32; no 1-41729 nD 1.41931 np 1.42416 1.42775; RO 69.22 RD 69-51 Rp 70.22 Rae 70.68; Ra,-c 1.52 R+Q 1.00; Mn?' 377.99. Densities determined 4:' 0.9681 dj?'2' 0.9324 d:?" 0.9128 d:?03' 0.8818. 15.3" 14.93 14.69 0.9721 26.74 623.0 87.3" 12-60 12-36 0.9109 21.08 626.5 61.2 13.48 13.24 0.9329 23.13 626.0 120.6 11.36 11.12 0,8815 18.35 625.3 Mean 685.2 [Evans Davies and Jones Zoc. cit. give b. p. 138'/10 mm. G?0-9617 0.9665 (extrap.) nt5' 1-4152 n$ 1.4173 &25'p ,.RC69.358 RD89.666 Rp 70-383.1 49. Tri-n-amyZ ovthophosphate. B. p.. 167"/5 mm. (through an all-glass apparatus ; rubber bungs are slightly attacked); M 308.39; no 1.42975 nD 1-43188 nF 1-43701 no# 1.44085; Rc 82.88 RD 83-24 RF 84.09 Ran 84.74; Ra*-c 1.86 RF-C1-21; Mnr 441.58. Densities determined dt!' 0.9608 d:?:" 0.9285 d::"" 0.9083 di?o'6' 0.8816. The parachor results were unsatisfactory the parachor increasing appreciably with rise of temperature. [Evans, Davies and Jones loc. cit. give b. p. 225"/50 mm. & 0.9497 &!" 0.9542 (extrap.),nE5*1.4262 ng' 1.4283 np' 1.4332; Rc 83.209 RD83.567 RF 84.401.] Acknowledgment is made to D. I. Coome M.Sc. for the preparation and preliminary measurements upon compounds 12 13 15 31-38 43-47 and 49.The authors' thanks are tendered to Eastman Kodak Co. for the supply of the pure thiols sulphides and disulphides and to Imperial Chemical Industries Ltd. for the liberal grants which have defrayed most of the heavy cost of the research. WOOLWICH LONDON, POLYTECHNIC S.W. 18. [Received November 2nd 1942.1

ISSN:0368-1769    

DOI:10.1039/JR9430000016

出版商:RSC    

年代:1943

数据来源: RSC