EXCHANGE 
 
A Study of the Reactions of Normal Butyl 
 Mercaptan and Some of its Derivatives 
 
 DISSERTATION 
 
 SUBMITTED TO THE BOARD OF UNIVERSITY STUDIES OF THE 
 
 JOHNS HOPKINS UNIVERSITY IN CONFORMITY WITH THE RE- 
 
 QUIREMENTS FOR THE DEGREE OF DOCTOR OF PHILOSOPHY 
 
 BY 
 THOS. C. WHITNER, JR. 
 
 June, 1920 
 
 EASTON, PA.; 
 
 ESCHENBACH PRINTING COMPANY 
 1921 
 
A Study of the Reactions of Normal Butyl 
 Mercaptan and Some of its Derivatives 
 
 DISSERTATION 
 
 SUBMITTED TO THE BOARD OF UNIVERSITY STUDIES OF THE 
 JOHNS HOPKINS UNIVERSITY IN CONFORMITY WITH THE RE- 
 QUIREMENTS FOR THE DEGREE OF DOCTOR OF PHILOSOPHY 
 
 BY 
 
 THOS. C. WHITNER, JR. 
 \* 
 
 June, 1920 
 
 EASTON, PA.; 
 
 ESCHENBACH PRINTING COMPANY 
 1921 
 
CONTENTS 
 
 Acknowledgment 2 
 
 Introduction 3 
 
 Experimental : 
 
 Reactions of Butyl Mercapto-ethyl Alcohol 4 
 
 Reactions with Alkyl Halides 6 
 
 Reactions with Aldehydes and Ketones 6 
 
 Sulphones 7 
 
 Mercuric Iodine Derivatives 8 
 
 Discussion 9- 
 
 Biography 10 
 
 462004 
 
ACKNOWLEDGMENT. 
 
 This investigation was undertaken at the suggestion of Professor Reid 
 and carried out under his direction. I gladly avail myself of this oppor- 
 tunity to express to him my sincere appreciation of the help which he 
 gave. I wish also to thank Professors Frazer, Patrick, and Lovelace for 
 instruction and encouragement received from them. 
 
A SULFIDE ALCOHOL, OR BUTYL MERCAPTO-ETHYL 
 
 ALCOHOL. 
 
 In a recent article from this laboratory, 1 the acid, CH 3 CH 2 CH 2 CH 2 - 
 SCH 2 COOH, was studied with respect to the influence of the sulfur atom 
 on the chemical and physical properties. In the present investigation, 
 the corresponding alcohol, CH 3 CH 2 CH 2 CH 2 SCH 2 CH 2 OH, has been 
 studied with the same object in view. 
 
 This alcohol is obtained readily by the action of ethylene chlorohydrine 
 on the sodium salt of butyl mercaptan in water solution. It is a color- 
 less oil boiling at 92-3 at 3 mm. In its physical properties and in its 
 reactions, it resembles one of the hgiher alcohols, though some differences 
 are found. Its odor suggests a higher alcohol and a sulfide, though the 
 odor of its acetate is much more like that of an acetate of a higher alcohol. 
 The chloride and bromide are readily prepared from the alcohol by the 
 usual methods, but it shows very slight tendency to combine with phthalic 
 anhydride. The sulfur atom appears to exercise somewhat the same 
 influence on the mobility of the groups in the 0-position as in the sulfide 
 acid and in mustard gas, though the influence is less evident here. The 
 acetate of this alcohol is stable, while the diacetate corresponding to 
 mustard gas is very unstable. 
 
 From the bromide, BuSCH 2 CH 2 Br, the sulfide, BuSCH 2 CH 2 SBu, was 
 readily obtained, but the corresponding sulfide ether, BuSCH 2 CH2OEt, 
 could not be prepared by heating the bromide with sodium ethylate, 
 vinyl-butyl sulfide, BuSCH : CH2, was formed instead. This substance 
 added hydrobromic acid readily to give the original bromide instead of the 
 secondary bromide, BuSCHBrCHg which we desired. 
 
 The properties of the alcohol and its derivatives are brought together 
 in the following table. 
 
 TABLE I. 
 
 ,0 ,25 
 
 Compound. B. p. <*<) ^25' n D 20. 
 
 BuSCH,CHjOH 92-3 at 3 mm. 0.9828 0.9693 1.4800 
 
 BuSCH 2 CH,OCOCH, 84 at 4 mm. 1.0043 0.9875 1.4648 
 
 BuSCHjCHjCl 68 at 6 mm. 1.0315 1.0101 1.4825 
 
 BuSCH 2 CH 2 Br 74 at 3 mm. 1.2308 1.2089 1.6740 
 
 1 Uyeda and Reid, /. Am. Chem. Soc., 42, 2385 (1920). 
 
6 
 
 Experimental. 
 
 The Alcohol, Butyl Mercapto-ethyl Alcohol. To 40 g. of caustic soda and 90 g. 
 of butyl mercaptan dissolved in 250 cc. of water, 80 g. of chlorohydrine was added. 
 The mixture was boiled under a reflux condenser for one hour and distilled with steam 
 to eliminate impurities. The alcohol remained behind; it was separated, dried, and 
 distilled in vacuo. Yield, 108 g. 
 
 The Acetate, Butyl Mercapto-ethyl Acetate. The alcohol was mixed with an 
 equal amount of acetyl chloride and the mixture allowed to stand for some hours. The 
 product was washed thoroughly with water, then dried over calcium chloride and dis- 
 tilled. 
 
 Analysis. Subs., 1.7100: 0.5441 g. KOH required for saponification. Calc. : 0.5448. 
 
 The Chloride, Butyl Mercapto-ethyl Chloride. A mixture of 30 g. of the alcohol 
 and 32 cc. of cone, hydrochloric acid was boiled under a reflux condenser for 4 hours, with 
 the further addition of 10 cc. of the acid during this operation. The mixture was ho- 
 mogeneous at first, but soon separated into 2 layers. The chloride was washed thor- 
 oughly, dried, and distilled. 
 
 Analysis. Calc.: Cl, 23.25. Found: 22.96. 
 
 The Bromide, Butyl Mercapto-ethyl Bromide. This compound was prepared in 
 several slightly different ways. (1) A mixture of 30 g. of the alcohol and 72 g. (2 mole- 
 cules) of constant-boiling hydrobromic acid was boiled for 8 hours; yield, 13 g. (2) 
 Dry hydrogen bromide was passed for 3 hours into 50 g. of the alcohol which was kept 
 cold; yield, 20 g., or 27%. (3) Dry hydrogen bromide was passed for 3 hours into a 
 mixture of 50 g. of the alcohol and a little red phosphorus kept at a temperature of 
 30-40; yield, 30 g., or 41%. (4) A mixture of 90 g. of the alcohol and 125 g. of con- 
 stant-boiling hydrobromic acid (3.5 molecules) was boiled for 3 hours under a reflux 
 condenser; yield, 68 g., or 51%. In all cases the layer of bromide was separated, 
 washed carefully, and distilled. 
 
 Analysis. Calc.: Br, 40.57; S, 16.28. Found: Br, 40.40; S, 15.93. 
 
 Dibutyl Ethylene Sulfide, BuSCH 2 CH 2 SBu. To a solution of 5 g. of sodium 
 in 100 cc. of alcohol, 20 g. of butyl mercaptan and 40 g. of the bromide just described 
 were added. The mixture was refluxed for a time, water was added, and the oily layer 
 was separated, dried and fractioned. The main portion boiled at 130 at 5 mm. pres- 
 sure and proved identical with a product, to be described later, which was obtained by 
 the action of ethylene bromide upon butyl mercaptan. 
 
 Vinyl-butyl Sulfide. To 75 cc. of alcohol in which 6 g. of sodium had been dis- 
 solved, 35 g. of the bromide was added and the mixture was heated for 30 minutes. 
 Water was added and the oily layer washed and dried . Under atmospheric pressure, 
 this began to distil at 150 , but the boiling point rose steadily to 217. Helfrich and 
 Reid 1 had a similar experience with vinyl sulfide. Several preparations were made, 
 but no material of constant properties could be obtained. That vinyl-butyl sulfide 
 was present seems to be shown by the following experiments. Bromine was absorbed 
 rapidly by a chloroform solution but the desired dibromide could not be obtained; 
 complicated reactions appear to take place. A chloroform solution of the product 
 was saturated with hydrobromic acid. After the solution had stood during the night, 
 it was saturated with hydrogen bromide again. When the chloroform was removed 
 and the product had been fractioned in vacuum, an oil' boiling at 75 under 4 mm. 
 pressure was obtained, d<J 1.2253, and dff 1.2075, and contained 40.38% of bromine 
 instead of 40.57 as calculated for the monobromide. Since the density does not agree 
 with that of the original primary bromide, it was hoped that it might be the secondary 
 
 1 Helfrich and Reid, J. Am. Chem. Soc., 42, 1225 (1920). 
 
bromide, BuSCHBrCH 3 , which, according to Markownikow's rule, 1 would be expected. 
 To test this conclusion, the product was made to react with the sodium compound of 
 butyl mercaptan as described above. A bis-sulfide was obtained, which boiled at 106-7 
 at 3 mm. This, on oxidation, gave a sulfone melting at 180 which is known to be 
 BuSO 2 CH 2 CH 2 SO 2 Bu, instead of the sulfone (BuSO 2 ) 2 CHCH 3 which melts at 64. 
 This showed that hydrobromic acid had added to regenerate some at least of the orig- 
 inal primary bromide. Since the yields of these sulfones are always low, the presence 
 of some of the isomeric bromide is not excluded. 
 
 The Iodide. An attempt was made to obtain this compound by allowing a mixture 
 of 15 g. of the chloride, 20 g. of sodium iodide and 80 cc. of alcohol to stand during the 
 night. Water caused the formation of an oily layer which was washed, and dried over 
 calcium chloride. This liquid contained 41.89% of iodine' instead of 52.02% calculated 
 for the iodide. An attempt was made to distil it in vacua, but decomposition took place 
 accompanied by deposition of iodine on the sides of the flask. A viscous oil was left 
 as a residue. This was washed with a solution of thiosulfate and the iodine in the 
 residual oil was determined. The iodine content was found to be 76.33%, which agrees 
 with 76.48% calculated for CJIgSI-jCH^CHjI, though this agreement is regarded as 
 largely accidental in view of the properties of the residue. Rathke 2 has prepared an 
 analogous compound, (C 2 H 6 ) 2 SIj. 1 
 
 The peculiar difficulty encountered with the iodide may be related to the known 
 tendency of sulfides to form sulfonium compounds with alkyl iodides. A complicated 
 sulfone might be formed by the union of the iodide with itself. This would be de- 
 composed by heat, and liberated iodine might combine with some of the iodide. 
 
 Summary. 
 
 The following compounds have been prepared: tt.C 4 H 9 SCH 2 CH 2 OH, 
 butyl mercapto-ethyl alcohol; w.C 4 H9SCH 2 CH 2 OCOCH3, butyl mercapto- 
 ethyl acetate; tt.C 4 H 9 SCH 2 CH 2 Cl, butyl mercapto-ethyl chloride; w.C 4 H 7 - 
 SCH 2 CH 2 Br, butyl mercapto-ethyl bromide. 
 
 SOME DERIVATIVES OF BUTYL MERCAPTAN AND THEIR 
 MERCURIC IODIDE COMPOUNDS. 
 
 Most of the investigations concerned with mercaptans have been lim- 
 ited almost exclusively to the lower members of the series, viz., to methyl 
 and ethyl mercaptans. The following investigation was undertaken to 
 extend our knowledge to the higher members of the series, particularly 
 to normal butyl mercaptan and to accumulate further information about 
 compounds which contain the sulfide grouping more than once, or this 
 group with other groups. 
 
 1 Ber., 2, 660 (1869); Ann., 153, 256 (1870). 
 
 2 Rathke, Ann., 152, 214 (1869). 
 
The work may be divided into 2 parts: compounds prepared by the 
 action of the sodium salt of butyl mercaptan with halides; and those pre- 
 pared from butyl mercaptan with aldehydes or ketones. 
 
 The sulfones of these sulfides, as well as their mercuric iodide com- 
 pounds, have been prepared, partly for their own sakes and partly to fur- 
 nish solids for identification and for analysis. 
 
 Experimental. 
 Reactions with Halides. 
 
 The mercaptan was dissolved in from 3 to 5 parts of 95% alcohol, 
 together with an equivalent amount of sodium hydroxide, and to this 
 mixture the calculated amount of the halide was added. The mixture 
 was heated till the reaction seemed to be complete, diluted with water, 
 and the oil separated. From the less volatile oils, impurities were elim- 
 inated by steam distillation. The oils were dried over calcium chloride 
 and fractioned, usually in vacuo. It is hard to give yields on account of 
 distillation losses, but they were all fairly good. The halides used were 
 ethyl iodide, methylene chloride, ethylene bromide, chloro-methylethyl 
 ether and phenacyl chloride. The following compounds have been 
 prepared: ethylbutyl sulfide; methylene dibutyl sulfide or dibutyl mer- 
 capto-methane; ethylene dibutyl sulfide or o;,/3-dibutyl mercapto-ethane; 
 ethoxy-methyl-butyl sulfide; and butyl phenacyl sulfide. Their proper- 
 ties are given in Table I. 
 
 TABLE I. 
 
 jO j25 ^200 
 
 Formula. B. p. C. Q . n D . 
 
 C 2 H 6 SC 4 H9 ....................... 144-5 0.8763 0.8574 1.6527 
 
 C 4 H9SCH 2 SC 4 H9 .................. 146 at 43 mm. .9482 .9,332 1 .4964 
 
 C 4 H 9 SCH 2 CH2SC 4 H9. . .. ........... 129-30 at 5 mm. .9524 .9389 1 .4962 
 
 C 2 H 5 OCH 2 SC 4 H9 .................. 179-81 0.9054 0.8877 1.4502 
 
 140 at 3 mm. 1.0712 1.0589 1.5050 
 
 Reactions with Aldehyde and with Ketones. 
 
 The reactions of butyl mercaptan with aldehydes and with ketones 
 were all carried out under the same conditions. The aldehyde, or ketone, 
 was mixed with 2 equivalents of the mercaptan and the mixture heated 
 to 50-60 under a reflux condenser for several hours, while a slow current 
 of dry hydrogen chloride was passed into the liquid. With acetaldehyde, 
 application of heat was not required. Water was added to the product, 
 which was then distilled with steam to rid it of volatile impurities. The 
 residual oil was separated, dried over calcium chloride and fractioned in 
 vacuo. The yields of purified products were 50 to 60% of the calculated 
 amounts. The following compounds have been prepared: acetaldehyde- 
 dibutyl mercaptal; acetone-dibutyl mercaptol; benzaldehyde-dibutyl mer- 
 captol; and acetophenone dibutyl mercaptol. Their physical properties 
 are given in Table IT. 
 
9 
 TABLE II. 
 
 Formula. B. p. C. dg. da|. D- 
 
 CH 3 CH(SC 4 H 9 )j 105 at 3 mm. 0.9399 0.9272 1.4900 
 
 (CH 3 )C(SC4H,) 2 110 at 4 mm. 0.9304 0.9215 1.4842 
 
 C 6 H 6 CH(SC4H 9 )j 167 at 4 mm. 1.0180 0.9999 1.4445 
 
 C 9 H 6 CH 3 C(SC4H,), 167-8 at 3 mm. 1.0241 1.0110 1.5535 
 
 Sulfones. 
 
 Dibutyl Sulfone Methane, CJ^SOzCHzSC^Hs. Various methods 
 of oxidation were tried, but none was found entirely satisfactory; the yields 
 were generally poor. 
 
 Four g. methylene dibutyl sulfide was added to 150 cc. of water con- 
 taining 16 cc. of sulfuric acid and 25 g. of sodium dichromate. A vigorous 
 reaction took place, after which the mixture was boiled for 45 minutes. 
 As the liquid cooled, the sulfone separated. After recrystallization from 
 hot water, it formed large white plates. The same product was obtained 
 when 5 g. of the sulfide was dropped into 20 cc. of fuming nitric acid. 
 The sulfone separates when this mixture is poured into water. The 
 yield was about 2 g. by each method. The melting point is 182. 
 Calc.: S, 25.03. Found: 25.06. 
 
 Ethylene Dibutyl Sulfone, CiHsSC^CHzCHzSOzCiHg. Ten cc. of the 
 sulfide was added slowly to 20 cc. of fuming nitric acid, while the acid 
 was cooled and stirred. When this product was poured into water, 25 
 g. of the sulfone separated. Recrystallized from hot water, it melted 
 at 180. 
 
 Calc. : S, 23.73. Found: 23.65. 
 
 Ethylidene Dibutyl Sulfone, CHsCHCSC^C^V While a suspension 
 of 5 g. of the sulfide in 300 cc. of 2% sulfuric acid was stirred rapidly, a 
 5% solution of potassium permanganate was added to it slowly till the 
 pink color was permanent; then sodium sulfite was added to dissolve 
 manganese dioxide. The solution was evaporated to */ its volume, 
 filtered and cooled. This caused the separation of the sulfone as white 
 needles. It melts at 64. 
 
 Calc.: S, 23.73. Found: 23.97. 
 
 Benzylidene Dibutyl Sulfone, CeHaCHCSC^Hgk was prepared by the 
 same method. Yield, 0.2 g. from 5 g. of sulfide; m. p., 86. A better yield 
 (0.4 g from 3 g.) is obtained if a solution of the sulfide in 60 cc. of acetic 
 acid is treated first with water until an incipient turbidity appears, and 
 then slowly with pulverized permanganate. Occasionally some dil. sul- 
 furic acid should be added. When the calculated amount of permanganate 
 had been used the solution was diluted with 100 cc. of water, cooled and 
 filtered. The precipitate was extracted with boiling water from which 
 the sulfone crystallized as white needles. This is a modification of the 
 method employed by Hilditch. 1 No sulfones could be obtained from 
 1 Hilditch. J Chem. Soc., 93, 1524 (1908). 
 
10 
 
 the mercaptols made with acetone and with acetophenone ; oxidation 
 to sulfonic acids must have taken place. When the sulfur atoms are sep- 
 arated by 2 carbon atoms, RSCH 2 CH 2 SR', strong oxidizing agents may be 
 used. 
 
 Though all of the oxidation methods mentioned above were tried sul- 
 fones were not obtained from ethoxy-methyl-butyl sulfide, acetone-dibutyl 
 mercaptal and acetophenone dibutyl mercaptol. 
 
 Mercuric Iodide Derivatives. 
 
 It was expected that mercuric iodide would combine with these sulfides 
 1:1, but, except for the 2 sulfides, methylene dibutyl sulfide and ethylene 
 dibutyl sulfide, this was found not to be the case. In all other cases the 
 ratio of iodine to mercury in the product was less than 2 : 1, which implies that 
 combination takes place with mercuric rather than with mercurous iodide. 
 Except for ethyl-butyl sulfide, 2 mercuric iodide groups are taken up for 
 each atom of sulfur present. A part of the iodine may enter the molecule 
 by substitution and the other part remains in the mother liquor from 
 which the compounds separate. In a number of instances these mother 
 liquors were titrated for iodine and, in all cases, very nearly the calculated 
 amount of iodine was found. They were found to be acid to litmus. 
 The mother liquors from the 2 compounds with mercurous iodide men- 
 tioned above, contained no iodine. 
 
 To prepare these compounds, 2 to 5 g. mercuric iodide was suspended 
 in 50 cc. of acetone, and the sulfide was added slowly while the mixture 
 was shaken and cooled. The disappearance of red mercuric iodide de- 
 termined the end of the reaction. This required about 2 mols of the 
 sulfide to 1 mol of the mercuric iodide in the first 5 preparations and about 
 1:1 for the other 4. Sometimes white or yellow crystals appeared im- 
 mediately, while in some cases the addition of alcohol was necessary to 
 precipitate the compound. 
 
 The compounds which separated readily from acetone were recrystal- 
 lized from it, the others, from alcohol. 
 
 The compounds and their analyses are given in Table III. 
 
 TABUJ III. 
 
 Hg I 
 
 Color and M. p. calc. Pound. calc. Found. 
 
 Compound. form. C. %. %. %. %. 
 
 2C 2 H 6 SC 4 H 9 .3HgI white plates 163 49.38 49.14 32.06 32.33 
 
 C4H 9 SCH 2 SC 4 H 9 .HgI t small cryst. 89 31 .02 30 .85 39 .26 39 .22 
 
 C4HoSCH2CH,SC4H 5 .Hgl2 white plates 85 30 .36 30 .41 
 
 CsHeOCHISC^Hgl^ yellow plates 156 43.16 43.42 40.98 41.17 
 
 CH 6 COCH 2 SC 4 H 9 (HgI) 2 yellow plates 158 46.48 46.60 29.41 29.67 
 
 CH 8 CI(SC 4 H 9 )2(HgI) 4 yellow plates 138 48 .86 48 .83 38 .65 38 .44 
 
 (CH 2 I) 2 C(SC 4 H 9 )2(HgI) 4 yellow plates 159 45.30 45.50 42.97 42.68 
 
 C e H 6 CI(SC 4 H 9 )j(HgI) 4 yellow plates 86 47.08 47.17 37.23 36.93 
 
 C 6 H (CH 2 I)C(SC 4 H 9 ) 2 (HgI) 4 yellow plates 155 46.72 46.84 36.93 36.75 
 
 The sulfur in (1) was found to be 5.05, calc. 5.26%; and in (4) 3.45, calc. 3.33%. 
 
11 
 
 Discussion. 
 
 Phillips 1 has observed that methyl sulfide and cupric chloride do not 
 
 form (CH3) 2 S.CuCl 2 , but 2(CH 3 ) 2 S.2CuCl, to which the structural for- 
 
 CH 3 
 
 mula CICu.S - S.CuCl was assigned, since there is no indication that 
 
 CH 3 
 
 the copper has been reduced. Similarly, auric chloride unites with the 
 same sulfide to form ClAu.S(CH3) 2 . We may assume, with Phillips, 
 that the sulfur in our compounds has a valence of 4 and write : 
 
 Hgl CH 3 Hgl 
 
 Hgl I Hgl 
 
 Tschugaeff 2 has obtained crystalline derivatives of the type CuCl 
 RSCH 2 CH 2 SR which correspond with 2 of ours. 
 
 The only compound of a new type which we obtained is represented by 
 the formula 2C 2 H 6 SC 4 H9.3HgI, obtained from ethyl-butyl sulfide, which 
 is similar to 2(CH 3 ) 2 S.3HgCl 2 obtained by Phillips, except that in this 
 case we have mercuric iodide instead of mercurous iodide. 
 
 Summary. 
 
 A number of derivatives have been made from butyl mercaptan. The 
 following new compounds have been prepared : 
 C2H 5 SC 4 H 9 , 2C 2 H 5 SC 4 H 9 .3HgI 
 (C 4 H 9 S) 2 CH 2 , (C 4 H 9 S0 2 )CH 2 , (C 4 H 9 S) 2 CH 2 .HgI 2 
 (C 4 H 9 SCH 2 ) 2 , (C 4 H 9 S0 2 CH 2 ) 2 , (C 4 H 9 SCH 2 ) 2 .HgI 2 
 C2H 6 OCH 2 SC 4 H 9 , C 2 H 5 OCHISC 4 H 9 . (Hgl) 2 
 
 C 6 H 6 COCH 2 SC 4 H 9 , C6H 5 COCH 2 SO 2 C 4 H 9 , C6H 5 COCH 2 SC 4 H 9 (HgI) 2 
 CH 3 CH(SC 4 H 9 ) 2 , CH 3 CH(SO 2 C 4 H 9 ) 2 , CH 3 CH(SC 4 H 9 ) 2 (HgI) 4 
 (CH 3 ) 2 C(SC 4 H 9 ) 2 , (CH 2 I) 2 C(SC 4 H 9 ) 2 (HgI) 4 
 C 6 H 5 CH(SC 4 H 9 ) 2 , C 6 H 5 CH(S0 2 C 4 H 9 ) 2 , C 6 H 5 CI(SC 4 H 9 ) 2 (HgI) 4 
 C 6 H 6 (CH 3 )C(SC 4 H 9 ) 2 , C 6 H 5 (CH 2 I)C(SC 4 H 9 ) 2 (HgI) 4 
 
 1 Phillips, /. Am. Chem. Soc., 23, 256 (1901). 
 
 2 Tschugaeff, Ber., 41, 2226 (1908). 
 
BIOGRAPHY. 
 
 Thomas Cobb Whitner, Jr., was born at Atlanta, Georgia, February 7, 
 1893. His elementary education was received in the schools of that city. 
 He entered the Georgia School of Technology in 1909, from which he re- 
 ceived the degree of Bachelor of Science in Textile Engineering in 1914. 
 Two more years of study were spent at this same institution for which he 
 received the degree of Bachelor of Science in Chemistry in 1916. In 1917 
 he entered the Johns Hopkins University as a graduate student and has 
 continued his studies in Chemistry at this University for the past three 
 years. 
 
Gaylord Bros. 
 
 Makers 
 
 Syracuse. N. V. 
 PAT. JAN. 21,1908 
 
 4G2004 A 4 U/-T 
 
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