THE PREPARATION OF RENZO 
 DIOXANS 
 
 HY 
 
 ARTHUR WILLIAM SLOAN 
 
 THESIS 
 
 FOR THE 
 
 DEGREE OF BACHELOR OF SCIENCE 
 
 CHEMISTRY 
 
 COLLEGE OF LIBERAL ARTS AND SCIENCES 
 
 UNIVERSITY OF ILLINOIS 
 
 1922 
 

 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 ■ 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
ACKNOWLEDGMENT 
 
 The author wishes to extend his sincere thanks to 
 
 Dr. Roger Adams, who suggested, and has criticised 
 and supervised all the work of this problem. 
 
 
Digitized by the Internet Archive 
 in 2015 
 
 https://archive.org/details/preparationofbenOOsloa 
 
(i) 
 
 TABLE OP CONTENTS 
 
 Page 
 
 I* Introduction 1 
 
 II. Historical Part S 
 
 III. Theoretical Part 3-5 
 
 IY. Experimental Part 
 Preparation of: 
 
 (1) 5, 6 p-bromobenzo , 2-phenyl, 1, 3 dioxan 6 
 
 (2) 5, 6 p-brombenzo, 2-p-bromphenyl , 1, 3-dioxan. . . .7 
 
 (3) 5, 6 p-brombenzo, 2-p-ohlorphenyl, 1, 3-dioxan. . . 8 
 
 (4) 5, 6 p-brombenzo, 2- p phenylethylene , 1, 3-dioxan. 8-9 
 
 (5) 5, 6 benzo, 2-/3 phenylethylene, 1, 3 dioxan .... 9 
 
 (6) 5, 6 p-nitrobenzo , 2-p-bromphenyl, 1, 3-dioxan . . 10 
 
 (7) 5, 6 p-nitrobenzo, 2-p-chlorphenyl, 1, 3-dioxan. . 10 
 
 (8) 5, 6 p-nitrobenzo, 2 - [3 phenylethylene, 1, 3-dioxan 11 
 
 (9) 5, 6 p-methylbenzo , 2-phenyl, 1, 3-dioxan .... 12 
 
 (10) 5, 6 p-methyl, o-methoxybenzo , 2-phenol, 1, 3 
 
 dioxan 12 
 
 (11) 5, 6 benzo, 2-propyl, 1, 3-dioxan 13-14 
 
 (12) 5, 6 benzo, 1, 3-dioxan 14-15 
 
 (13) Homosaligenin 15-16 
 
 (14) p-brom8aligenin 16 
 
 (15) Butyl aldehyde 16-17 
 
 V. Bibliography 18 
 

 
 
 
 
 
 
 
 
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(1) 
 
 PART I 
 
 INTRODUCTION 
 
 The dioxans are a class of compounds of comparatively recent 
 origin. They are six membered rings in which there are four carbon 
 atoms and two oxygen atoms. Three types are possible: 
 
 </S> 
 
 y c x 
 
 c o 
 
 1 
 
 II 
 
 n 
 
 c v c 
 
 III 
 
 of which only members of types II and III are known at present. 
 
 Kreger 2 , in his work on the structure of disalicyl aldehyde, 
 found that saligenin would react with benzaldehyde to give a compound 
 having properties entirely similar to those of disalicyl aldehyde. 
 Prom this, he was led to prepare compounds from saligenin and 
 p-chlorbenzaldehyde , p-brombenzaldehyde , and p-nitrobenzaldehyde . 
 
 These compounds he showed to be of the type , the reaction 
 
 being: _ . 
 
 4 i X ^ (5 ’ 6 Be71550 ’ 2-phenyl^ 
 
 ° Q 1,3 dioxan. ) 
 
 0 CH r OH „ 
 
 OH + v 'c 
 H' 
 
 ‘k 
 
 OMWoje 
 
 H 
 
 The discovery of the reaction between benzaldehyde and sali- 
 genin has led to the work in this paper in which it was proposed to 
 study the reactions of substituted saligenins with substituted 
 benzaldehydes to see if the reaction were a general one, to determine 
 the effect of substituting groups on the reaction, and to see if 
 aliphatic aldehydes could be made to condense with saligenin in a 
 manner similar to that of aromatic aldehydes. 
 

 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
(2) 
 
 PART II 
 
 HISTORICAL PART 
 
 Henry 3 , in 1902, seems to be among the first to have prepared 
 a dioxan. His was the 1, 3-dioxan i 1 ° which he called tri- 
 methylene methylal. It was made by treating trimethylene glycol 
 with formaldehyde. Clarke 4 , in 1912, prepared the same compound by 
 treating trimethylene glycol with polyoxymethylene in the presence 
 
 C Hj'CHi 
 
 of orthophosphoric acid. He also prepared the 1, 4-dioxan i h ;i 
 by the method of Paworsky^, dehydrating ethylene glycol with sulfuric 
 acid. 
 
 Members of the benzo dioxans have been prepared by Borsche and 
 Berkhout^ by using substituted phenols instead of glycols, in the 
 presence of dilute sulfuric acid. By this method, Borsche and Berk- 
 hout have been able to prepare*. A 
 (Y“>. 
 
 C "1 CM. c L H v c H-w 
 
 i ii in rv v 
 
 They attempted to confirm the structure of I by making it from 
 p-nitro saligenin and formaldehyde, but failed because they could 
 not make pure p-nitro saligenin, a compound up to that time unknown. 
 
 Quite recently, Prins 7 has discovered another way to make 
 1, 3-dioxans, namely, by a reaction between unsaturated compounds and 
 formaldehyde in the presence of sulfuric acid, using acetic acid as 
 the solvent. Prom styrolene, anethol and isosafrol, he gets respec- 
 tively : 
 
 <Z> CH-CH, 
 
 O c ►‘x. 
 
 chj0Och-ch-ch 3 or ch 3 o<c> ch - ch ch } } 
 
 O CH V CM- ° 
 
 « \ 
 CH, — O 
 
 '*■ I 
 
 O 
 
 and 
 
 or C ^X) 
 
 O CH X CHi 6 
 
 I 
 
 CH 
 l 
 
 C* x ~ 6 
 
 O - CH, 
 

 
 
 
 
 
 
 
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( 3 ) 
 
 PART III 
 
 THEORETICAL PART 
 
 Some of the reactions between saligenin and substituted ben- 
 zaldehydes go with the greatest ease, the saligenin and aldehyde 
 merely being heated on the steam bath until they melt together, and 
 then allowing them to cool for several hours, to solidify. In using 
 benzaldehyde and nitrobenzaldehyde , some benzoic acid should be 
 used as a catalyst, and for these two aldehydes, longer heating on 
 the steam bath is necessary. 
 
 Prom the foregoing, there is every reason to believe that 
 substituted saligenins should give compounds with substituted ben- 
 zaldehydes, or other aromatic aldehydes, the ease of formation 
 depending possibly upon the substituting groups present. 
 
 It was found that p-brom saligenin could be condensed with 
 benzaldehyde, p-brom benzaldehyde, p-chlorbenzaldehyde , and cinnamic 
 aldehyde; and p-nitro saligenin could be condensed with cinnamic 
 aldehyde. P-nitro saligenin seemed to give mostly resin with p-chlor- 
 benzaldehyde and p-brombenzaldehyde , but certain precautions in 
 manipulation might give these condensation products. An attempt to 
 condense homo saligenin with benzaldehyde was unsuccessful; so also 
 was an attempt to condense o, o-dimethoxy p-cresol with benzaldehyde. 
 With cinnamic aldehyde, tho it could be condensed with p-brom sali- 
 genin and p-nitro saligenin, it could not be condensed with saligenin 
 itself. 
 
 Since saligenin will condense with aromatic aldehydes, there 
 is some reason to believe that it will condense with aliphatic 
 aldehydes as well. However, it may be that a different type of 
 

 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
(4) 
 
 reaction is necessary to get the desired products. Borsche and Berk- 
 £ 
 
 hout° prepared 5, 6-p-nitrobenzo , 1, 3-dioxan by a reaction between 
 40 % formaldehyde and p-nitrophenol , in the presence of dilute sulfuric 
 acid. They explain the reaction: 
 
 * CH,0 
 
 0aN/\cM x OH 
 
 •OH 
 
 CHiO y 
 
 Theoretically, it should be possible to use phenol and formaldehyde 
 in a similar reaction and get 5, 6-benzo-l, 3-dioxan, but bakelite 
 resins form so easily that practically the reaction might not go. 
 
 3 
 
 Voorhout , in his study of the condensation products of phenol with 
 formaldehyde in the presence of dilute sulfuric acid was able to 
 isolate only dioxydiphenylme thane and some of its polymers. 
 
 Since dioxans are acetals, there is the possibility of making 
 them by the use of the acetal reaction. An attempt to condense 
 
 Q 
 
 saligenin and formaldehyde, lasing Fischer and Glebe 1 s method where 
 CaOlg is used as a dehydrating agent, gave no product. The reaction 
 should have been tried with ZnOlg as a catalyst, or by using dry 
 benzene or ether as the solvent for the formaldehyde, but these 
 attempts were not made. 
 
 Using the general reaction for condensing saligenin with 
 benzaldehyde , efforts were made to get butyl aldehyde to condense 
 with saligenin; but tho dilute and concentrated hydrochloric acid, 
 dilute sulfuric acid, and benzoic acid were used in various trials 
 as catylysts, and a trial was made without any catalyst, no product 
 of proved structure could be obtained, altho in all cases except the 
 latter, where no catalyst was used, a practically colorless oil was 
 obtained. This oil formed immediately in the presence of mineral 
 acids, but only during several hours heating in the steam bath, in 
 

 
 
 
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(5) 
 
 the presence of benzoic acid, and not at all in the absence of cat- 
 alysts. It boiled all the way from 70° to 180°C., giving a fair 
 fraction at 167°C. Comparing the 5, 6-p-nitrobenzo - 1, 3-dioxan 
 prepared by Borsche and Berlchout 6 , a solid melting at 144°-145°, one 
 would expect the condensation product of saligenin with butyl 
 aldehyde, 5, 6-benzo, 2-propyl, 1, 3-dioxan, to be a solid at room 
 temperature. The oil actually obtained would not solidify even in 
 an ice salt mixture. 
 

 
 
 
 
( 6 ) 
 
 PART IV 
 
 EXPERIMENTAL PART 
 
 Preparation of 5, 6-p-brombenzo , 2-phenyl, 1,3-dioxan. 
 
 2 g. (I mol) p-bromsaligenin and 1 g. (1 mol) benzaldehyde 
 were mixed in a 200 cc. round bottomed flask fitted with a reflux 
 condensing tube and heated on the steam bath for 20 minutes. The 
 flash was then allowed to stand at room temperature for 3 hours, 
 during which time, the liquid solidified to a crystalline mass. This 
 was broken up with a stirring rod, and 50 cc. of 10$ NaCOg sol. were 
 added. After thoro shaking, the insoluble product was filtered off 
 and washed with water. It was then crystallized by dissolving in 
 35 cc. hot 95$ alcohol, adding water until the solution became 
 milky, heating until clear, then allowing the solution to stand at 
 room temperature. By the end of a half hour, a white crystalline 
 precipitate had separated out. The mixture was cooled in an ice 
 bath filtered. Yield 1.5 g. Evaporation of the filtrate and 
 recrystallization of the residue from a few cc. of alcohol gave 0.3g. 
 additional product. Yield 60$. M.P. 82° - 83°. Recrystallization 
 from 95$ alcohol raised the melting point to 83°-84°. 
 
 Repeated trials using benzoic acid as a catalyst did not seem 
 to affect the reaction or the yields. 
 
 The product is quite soluble in alcohol and some of it is 
 lost during crystallization. 
 
 Analysis - 
 
 Substance: 0.5000 g. 
 
 Calc, for Cl4Hn02Br: C - 0.2887 g. 
 
 Pound: 0.2900 g. 
 

 
 
 
 
 
 
 
 
 
 
 
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( 7 ) 
 
 Analysis ( Cont.) 
 
 Pound: 650.1 cc. of COg at 741.0 mm. and 31.5°C. collected 
 over water. 
 
 Wt. C per cc. of CO2 - 0.4461 mg. 
 
 Preparation of 5 , 6-p-brombenzo , 2-p-bromphenyl, 1, 3 dioxan . 
 
 2 g. (1 mol) of p-brom saligenin and 1.8 g. (1 mol) p-brom- 
 benzaldehyde were mixed together and heated on the steam bath for 5 
 minutes. The mixture, which at first melted down somewhat, soon 
 became a solid mass. It was allowed to stand at room temperature for 
 10 minutes., then 100 cc. of 10$ Na2C03 solution were added. After 
 stirring well, the insoluble product was filtered off and washed with 
 water. Yieldcrude product 3.2 g. , 89$. It was not entirely soluble 
 in 60 cc. of hot alcohol, but without filtering the solution, water 
 was added until it became milky, and the mixture allowed to cool at 
 room temperature for several hours. A mass of flaky white crystals 
 separated out. These were filtered and washed with 95$ alcohol. 
 
 Yield 2.3 g. M.P. 140°-142.5°. Recrystallization from 95$ elcohol, 
 filtering off the insoluble matter, gave a M.P. 141°-142°. 
 
 Analysis: - 
 
 Substance: 0.5000 g. 
 
 Calc, for C^H^OgBrg : 0 - 0.2271 g. 
 
 Pound: C - 0.2252 g. 
 
 506.8 cc. of CC^ at 738.5 mm. and 31.5° collected over 
 water. 
 
 Wt. G per cc. of CO2 - 0. 4444 mg. 
 

 
 
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( 8 ) 
 
 Preparation of 5, 6-p-brombenzo , 2 p-chlorphenyl, 1,3-dioxan . 
 
 2 g. ( 1 mol) p-bromsaligenin and 1.4 g. (mol) p-chlor 
 benzaldehyde were mixed and heated on the steam hath for 5 minutes. 
 The mass at first melted do wn somewhat and then solidified. It was 
 allowed to stand at room temperature for 30 minutes, and then 100 cc. 
 of 10$ UagOOg solution were added. The insoluble product was broken 
 up with a stirring rod, filtered off and washed with water. Yield 
 crude product 2.9 g. , 91$. It was not entirely soluble in 60 cc. of 
 alcohol, but without filtering, water was added until the solution 
 became milky, heat applied until it was clear, and the resulting 
 solution allowed to stand at room temperature several hours. The 
 crystals formed were filtered off and washed with 95$ alcohol. 
 
 Yield 2.3 g. M.P. 144.5 - 146°. Recrystallization from 95$ alcohol, 
 filtering off the insoluble portion, gave a M.P. 145°-146° 0. 
 
 Analysis: - 
 
 Substance: 0.5000 g. 
 
 Oalc. for C^H^oOgClBr : 0 - 0.2581 g. 
 
 Pound: C - 0.2591 g. 
 
 584.4 cc. of COg at 741 mm. and 32.5° 0. collected 
 over water. 
 
 Wt. 0 per cc. of 00g = 0.4433 mg. 
 
 P- 
 
 Preparation of 5, 6-.brombenzo , 2- f 3 phenylethylene , 1,3-dioxan . 
 
 2 g. (1 mol) p-bromsaligenin and 1.3 g. (1 mol) of cinnamic 
 aldehyde were mixed and heated on the steam bath for 15 minutes. 
 
 A uniform melt resulted. It was allowed to stand at room temperature 
 for 2 hour s , during which time, it largely solidified. The mass was 
 broken up and 100 cc. of 10$ Nag CO^ solution added. The insoluble 
 

 
 
 
 
 
 
 
 
 
 
 
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(9) 
 
 product was filtered off and washed with water. Yield crude product 
 1.9 g. , 61 $. This was entirely soluble in 30 cc. hot 95$ alcohol. 
 Water was added until the solution became milky, heat applied to get 
 a clear solution, and the latter allowed to stand. at room temperature 
 for several hours. The white, flaky, crystals which formed were 
 filtered off and washed with 95$ alcohol. Yield 1.0 g. M.P. 115°r 
 118°. Recrystallization from 95$ alcohol gave a M.P. 118°-120°. 
 
 Analysis - 
 
 . 
 
 Substance: 0.4000 g. 
 
 Calc, for Cl6%302 Br : ® ~ 0.2423 g. 
 
 Pound: C - 0.2430 g. 
 
 537.2 oc. of COg at 741.2 mm. and 29.3° C. collected 
 over water. 
 
 Wt. of C per cc. COg = 0.4522 mg. 
 
 Preparation of 5,6-benzo, 2- phenylethylene, 1, 3-dioxan . 
 
 2 g. (1 mol) of saligenin and 2.2 g. (1 mol) of cinnamic alde- 
 hyde were mixed and heated on the steam bath for 10 minutes. Complete 
 solution resulted. It did not solidify, however, on two days stand- 
 ing at room temperature. 50 cc. of 10$ NagC 03 solution were added, 
 without any apparent change in the viscous liquid. 
 
 When the NagC 03 solution was separated off and neutralized 
 with acetic acid, a large part of the saligenin was recovered, show- 
 ing that no reaction had taken place. 
 
 The experiment was repeated using benzoic acid as a catalyst 
 and allowing the mixture to remain on the steam bath for 4 hours, 
 but there was no difference in the result. 
 

 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
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( 10 ) 
 
 Preparation of 5, 6-p-nitrobenzo , 2-p-brompfaenyl, 1,3-dioxan . 
 
 1 g. (1 mol) p-nitro saligenin^ and 1.1 g. (1 mol) p-brom- 
 benzaldehyde , and 0.25 g. of benzoic acid were well mixed and heated 
 on the steam bath for 5 minutes. One minute's additional heating 
 over a very small flame was necessary to cause complete solution. 
 
 The melt was allowed to stand for 15 hours at room temperature. No 
 reaction seemed to have taken place so the mixture was again melted 
 over a small flame and heated for 3 hours. Too much heat was used 
 however, and a small amount of charring occurred on one side of the 
 flask. The melt was again allowed 24 hours to solidify. Then 50 cc. 
 of 10$ Na 2 C 03 solution were added and the solid mass broken up. 30cc 
 of ether were shaken with the mixture to extract the desired product, 
 but the water insolbule portion was ether insoluble also. The ether 
 extract on evaporation left only a small amount of yellow gummy 
 residue. The insoluble substance was filtered off and washed with 
 water. It was taken up in 10 cc. of hot 95$ alcohol and precipitated 
 by addition of water to produce milkness, heating until the solution 
 became clear, then cooling in ice. The yellow flocculent precipitate 
 which separated out changed mostly to a gummy mass when allowed to 
 stand over night, part of which would not redissolve when heated with 
 more alcohol. Reprecipitation in the same way as before gave mostly 
 the same brownish gum. If the yellow precipitate were the desired 
 product, it was a very poor yield. The gum was probably a nitrosali- 
 genin resin formed as a result of too much heating. 
 
 Preparation of 5, 6-p-nitrobenzo , 2-p-ohlorphenyl , 1,3-dioxan . 
 
 1 g. (1 mol) p-nitrosaligenin and 0.85 g. (1 mol) p-chlorben- 
 zaldehyde and 0.25 g. of benzoic acid were well mixed and heated on 
 
 the steam bath for 5 minutes. Additional heating over a very small 
 

 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
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( 11 ) 
 
 flame for 1 minute was necessary to cause complete melting. Cooling 
 for 15 hours seemed to have produced no change, so the mixture was 
 again heated over a small flame for 3 hours, then allowed to stand 
 a day at room temperature. The solid mass which had formed was 
 ■broken up with a stirring rod. 50 cc. of 10# Fa 2 C 03 solution were 
 added, and after shaking, the insoluble product was filtered off and 
 washed with water. Yield crude product, 1.6 g. It was entirely 
 soluble in 15 cc. of hot 95# alcohol, but came down as a yellow 
 flocculent precipitate when chilled in ice. Upon standing, however, 
 it soon changed to a gammy mass, which was not entirely soluble when 
 reheated with alcohol. The soluble portion was reprecipitated by 
 by addition of water to the alcohol solution, cooling to room temper- 
 ature for 1 hour. Again, most of the flocculent precipitate changed 
 to a brown gum. Lack of p-nitrosaligenin to repeat the experiment 
 prevented the identification of this yellow precipitate as the 
 desired product. 
 
 Preparation of 5, 6-p-nitrobenzo , 2-/# phenylethylene 1, 3 
 dioxan . 1 g. (1 mol) p-nitro saligenin and 0.8 g. (1 mol) cinnamic 
 aldehyde, and 0.25 g. of benzoic acid were w&l mixed and heated on 
 the steam bath for 10 minutes. Complete melting resulted. After 
 standing for 15 hours at room temperature, the aldehyde appeared to 
 be still unreacted, so the mixture was again heated on the steam 
 bath for 3 hours, and let stand at room temperature for a day. 50 cc 
 of 10# NagCO^ solution were added, and the insoluble product filtered 
 off and washed with water. Yield crude product 0.9 g. This was 
 soluble in 10 cc. of hot 95# alcohol, but gave no precipitate on 
 cooling to room temperature. Addition of water to the hot solution 
 and cooling to room temperature for 1 hour brought down a soft yellow 
 

 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
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( 12 ) 
 
 precipitate, without the presence of any gum. Yield 0.3 g. M.P. 
 
 135. 5°-136.5° It was not crystallized a second time. 
 
 Analysis- 
 
 Substance : 0.2000 g. + 0.3000 g. Benzoic Acid. 
 
 Calc, for C 16 H 13 04 lT: C - 6.1356 g. 
 n " C 6 H 5 C0 2 H : C - 0.2066 g . 
 
 Total C - 0.3422 g. 
 
 Found: Total 0 - 0.3141 g. 
 
 698.8 cc. of COg at 741.2 mm. and 30.3°0 collected 
 over water. 
 
 Wt. of C per cc. of CO 2 = 0.4495 g. 
 
 Preparation of 5,6 p-methylbenzo , 2-phenyl, 1, 3-dioxan . 
 
 1 g. (1 mol) homosaligenin ( M.P. 98°-101°; Of. p. /J this paper 
 and 0.8 g. (1 mol) benzaldehyde were mixed and heated on the steam 
 hath for 10 minutes. Complete melting resulted. The mixture was 
 allowed to stand at room temperature for two days, during which time, 
 it did not solidify. 50 cc. of 10$ sol. FagQOg were added, hut there 
 was no apparent change in the original substances. Evidently, the 
 desired product was not obtained. 
 
 Preparation of 5, 6 p-methyl-o-methoxybenzo , 2-phenyl, 1, 3-dioxan 
 2 g. (1 mol) of 0 , o-dimethoxy p-cresol ( M.P. 127°-128°; 
 prepared by Auwer's method; Cf. preparation of homosaligenin , 
 p, 1 5 this paper) and 1.3 g (1 mol) of bengaldehyde were mixed and 
 heated on the steam bath for 2 hours. The melt was allowed to stand 
 for two days at room temperature, but it did not solidify. 50 cc. 
 of 10$ NagCOg sol. were added, but the original substances seemed to 
 
 be unchanged. Evidently the desired product was not obtained. 
 

 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
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(13) 
 
 Preparation of 5 , 6 benzo , 2-propyl, 1, 3-dioxan . 
 
 7 g. (1.3 mol) of butyl aldehyde were saturated with benzoio 
 acid (1 g. ) at room temperature, and to this solution, 10 g. (1 mol) 
 of saligenin were added. The resulting solution was heated at 55°0. 
 for 3it hours, using a small round bottomed flask and reflux condense]* 
 It was allowed to stand 11 hours at room temperature, but it did not 
 solidify. 300 cc. of 5$ NaOH sol. were added, and a colorless oil 
 separated out and collected on the surface. This was removed by 
 two extractions of the mixture with 100 cc. of ether. The ether 
 extract was then dried with CaOlg and the ether distilled off on the 
 steambath at 50°C. The slightly yellow liquid remaining in the 
 flask had a sickening sweetish odor. Yield crude product 6.5 g. It 
 boiled, upon distilling, from 70° to 180°, the temperature remaining 
 constant for some time at 167°, and again at 175°. The residue 
 left at 180° thickened, and became a gummy mass. 
 
 A repetition of the experiment, refluxing the mixture for 
 4 3/4 hours at 68° gave the same product. It was soluble in alcohol 
 but could be thrown out with water. 
 
 In another trial, dilute sulfuric acid was used as the 
 catalyst; 2 g. (1 mol) soligenin and 1.4 g (1.3 mol) butyl aldehyde 
 were dissolved in 10 cc. of benzene. A drop of dilute sulfuric acid 
 was added, and the solution shaken vigorously. Soon small particles 
 of the yellowish white oil began to separate out. 
 
 Without a catalyst, the reaction would not go. 10 g. (1 mol) 
 saligenin and 7 g. (1.3 mol) butyl aldehyde were mixed and refluxed 
 at 70° C. for 9 hours. At the end of this time, the odor of butyl 
 aldehyde was still present. After standing a week, 100 cc. of 10$ 
 
 Fa o C0„ sol. were added, but the insoluble portion did not seem to be 
 
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(14) 
 
 the same as that obtained in the presence of a catalyst. Presumably, 
 no reaction had taken place. 
 
 The experiment was repeated using hydrochloric acid as the 
 
 catylyst; 2 g. (1 mol) saligenin were dissolved in 1.1 g. (1 mol) 
 
 butyl aldehyde, and 1 drop of concentrated hydrochloric acid added. 
 
 An immediate reaction took place, with the separation of a yellowish 
 
 with sulfuric acid. 
 
 white oil, similar to the oil obtained above. It would not solidify 
 
 A 
 
 when chilled in an ice salt mixture to -1°C. 
 
 Preparation of 5, 6-benzo, 1, 5~dioxan . 
 
 0.2 g. of HC1 gas was dissolved in 10 cc. (0.86 mol) of 
 29% formaldehyde, 15 g. (1 mol) of saligeni n were then added, and 
 the mixture heated over a small flame. A reaction took place quite 
 suddenly, resulting in the entire solidification of the contents of 
 the flask to a hard, white, resinous mass. Very probably, it was a 
 resinifioation product of saligenin formed due to the presence of 
 hydrochloric acid. 
 
 Next a trial was run without a catalyst. (Compare Fischer and 
 Giebe's 9 method for making acetals) 10 g. (1 mol) saligenin were 
 dissolved in 20 co. (2.5 mol) of 29% formaldehyde solution with 
 gentle heating. To remove all the water, the solution was cooled 
 and 14.6 g. of CaClg were gradually added. Then the flask was stop- 
 pered and allowed to stand 40 hours. By this time, the odor of 
 
 formaldehyde was entirely gone. 50 cc. of water were added to the 
 
 in the water. 
 
 liquid mixture, which was entirely soluble. By extraction with ether 
 4 g. of saligenin were recovered, and the ether extract had the 
 strong odor of formaldehyde. An attempt to extract any reaction 
 product from the ether soluble residue with chloroform yielded only 
 

 
 
 
 
 
 
 
 
 
 
 
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(15) 
 
 a small amount of brown viscous liquid, smelling strongly of formalde- 
 hyde. From all evidences, the desired reaction had not taken place. 
 
 Preparation of Homosaligenin ^ 
 
 ! 
 
 22 g. (1 mol) sodium hydroxide were dissolved in 420 cc. (5 $ 
 sol) of water. In this, 54 g. (1 mol) p-eresol were dissolved. Then 
 70 cc. (1.2 mol) of 29$ formaldehyde were added, the solution well 
 shaken and allowed to stand at room temperature in a stoppered bottle. 
 By the end of three days, all odor of formaldehyde was gone. The so- 
 lution was nettralized (litmus) with 35 cc. (1.1 mol) glacial acetic 
 acid. This caused the precipitation of a large volume of fine creamy 
 product. Without filtering it off, 300 cc. of ether were added and 
 shaken with the mixture. The solid product collected in the ether 
 Layer, but did not dissolve. (Ether should dissolve homosaligenin but 
 lot o, o-dimethoxy, p-cresol) The ether layer was separated off and 
 bhe water solution again extracted with 200 cc. of ether. This was 
 igain separated off and added to the first ether extract, which was 
 then filtered from the creamy precipitate. This latter yielded 49 g. 
 rad gave a M.P. 90°-95°. Two recrystallizations from ethyl acetate 
 raised the M.P. to 127°-128°, but fc third crystallization had no furth • 
 jr effect. (o, o-dimethoxy, p-cresol should melt at 133°-134°) 
 
 The ether filtrate was evaporated to dryness, leaving a bfown- 
 .sh viscous residue which solidified partly as crystals upon chilling 
 rith ice. This was crystallized from 50 cc. of chloroform. The chlo- 
 roform filtrate upon evaporation gave 7 g. to 8 g. of residue mostly 
 3-cresol. 
 
 The crystallized product was only partly soluble in 75 cc. of 
 hot chloroform. The residue, 2 g. to 3 g. had a M.P. of 120°-125°. 
 

 
 
 
 
 
 
 
 
 
 
 
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 This second crystallization yielded 8.5 g. of product with a M.P. of 
 91°-92°. It was extracted twice with ether at room temperature, 
 filtering and evaporating to dryness after each extraction, and was 
 then recrystallized from chloroform. In this way, 2.8 g. of product 
 melting at 98°-101° were obtained. (Compare M.P. 105° as given by 
 Auwers) The ether insoluble residue, 3.3 g. , melted atl£0°-125°. 
 
 Preparation of p-bromsaligenin. 11 
 
 50 g. (1 mol) saligenin were dissolved in 1. of water, in 
 a 12 1. flask and immersed in a tub of ice and water to keep the 
 temperature between 5°-10°. The solution was stirred mechanically 
 while 9 1. of bromine water (containing 65 g. (1 mol) bromine) were 
 added in the course of 1 3/4 hours. The solution was filtered to 
 free it of a small amount of tar, and was then extracted with 3§- 1. 
 of ether, using two extractions. The ether extract was dried over 
 CaClg for 30 minutes, and the ether was distilled off. A yellow 
 liquid which solidified on cooling remained. One crystallization 
 from benzene gave 44 g. of white, shining, plate-like crystals, M.P. 
 103°-105°. Evaporation of the benzene gave 2 g. of the same product 
 56$ yield. A second crystallization of the product from benzene 
 raised the M.P. (Corr.) to 107°-109°. 
 
 This product gave a blue color with ferric chloride, but no reel 
 color with concentrated sulfuric acid as saligenin does. 
 
 Preparation of Butyl Aldehyde ^ 2 
 
 A 2 1. flask was fitted with a rubber stopper carrying a drop- 
 ping funnel, tube leading to the bottom of the flask, outlet tube to 
 a water condenser (120 cm. long), and a thermometer. 200 g. (2.7 mol) 
 of n-butyl alcohol were put into the flask and air bubbled thru it 
 

 
 
 
 
 
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 slowly. Then a mixture of 144 g. (0.48 mol) technical sodium 
 dichromate, 80 cc. of concentrated sulfuric acid and 250 cc. of 
 water were added in not quite a solid stream, keeping the temperatur 
 at 90°C. During this addition, air was gently sucked thru the 
 apparatus, hy attaching a suction pump to a 500 cc. suction filter 
 flask which was in turn connected to the condenser with an adapter 
 glass. 
 
 The distillate stopped coming over (at 90°) before all the 
 oxidizing mixture was used up, sq> the reaction was stopped. The 
 distillate, about 300 cc., was separated from the water layer, a 
 few cc. of aldehyde recovered from the water layer by salting out 
 with sodium chloride, and the aldehyde fractionated up to 85°0. The 
 residue, about 3 times the volume of the distillate, was put back 
 into the 2 1 . flask with the rest of the residue, heated to 85°, a 
 small current of air sucked thru, and the rest of the dichromate 
 run in in rapid drops. For this last run, more dichromate solution 
 (50 g. NagCrgOy 2HgO; 85 cc H 2 O; 27cc. cone. H 2 SO 4 ) was added. 
 
 The distillate was treated like the first distillate, the two 
 fractions boiling up to 85° being united. This fraction was separ- 
 ated from a small layer of water and dried for 15 minutes. over CaCl 2 - 
 
 It was then distilled with a good fractionating column and the 
 
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 fraction boiling 72°-74° was collected. Yield 45 g. 23 $ or 31.7$ 
 based on a recovery of 54 g. of alcohol. 
 
 The tarry material left in the 2 1. flask was discarded, and 
 the flask cleaned with steam and 10 $ sodium hydroxide. 
 
(18) 
 
 PART V 
 BIBLIOGRAPHY 
 
 1. Meyer and Jacobson - Lehrbuch der Organischen Chemie, Vol . II, 
 Pt. 3, Ab’t. 3, p. 1145. 
 
 2. Kreger, ,T The Structure of Disalicyl Aldehyde and the Formation 
 of Dioxans" , University of Illinois Thesis, 19E2. 
 
 3. Henry, Cent. Bl’t. 1902 II, 929. 
 
 Bui. Acad. Roy. Bel., 1902, 0. 460. 
 
 4. Clarke, Jour, of Chem. Soc. 101 , Pt. 2, 1803 (1912) 
 
 5. Faworsky, J. Russ. Phys. Chem. Soc. 38, 741 (1906) 
 
 6. Borsche and Berkhout, Ann. 330 , 82-107 (1904) 
 
 7. Prins, Ch. Abs. 14, 1119, 1662 (1920) 
 
 Chem. Weekblad 16, 1510-26 (1919) 
 
 Acad. Sci. Amsterdam 22, 51-56 (1919) 
 
 8. Voorhout, Ch. Abs. 14, 1119 (1920) 
 
 9. Fischer and Giebe, Ber. 30, 3054 (1897) 
 
 10. Auwers, Ber. 40, (2) 2531 (1907) 
 
 11. Auwers and Btlttner, Ann. der Chem. 302 , 131, 138 (1898) 
 
 12. Fosseck, M. fiir C. 2, 614 and 4, 660.