1080 GORDAN AND LIMPACH : RELATIONS BETWEEN PHYSICAL CXIV .-Some relations between Physical Constants nnd Constitution in Benxenoid Amines, Paint 11. BY PAUL GORDAN and LEONHARD LIMPACH. THIS paper is a continuation of the discussion of the relationship between " Melting Puints and Constitution i n some Amines " on which a preliminary note wag published in 1893 by W. R. E. Hodgkinson and L. Limpach (Proc., 9, 41). By replacing the benzenic hydrogen in formoanilide and acetanilide by methyl, 38 compounds can be obtained. If the number of intro- duced methyl groups be p, then the values 0 : 1 : 2 : 3 : 4 : 5 * represent the number, p, of the anilide, toluidides, xylidides, and amino-tri- methyl, -tetramethyl, and -pentamethyl derivatives respectively. The melting points of 36 of these 40 compounds have been actually determined, and are given in Table 1.This series, R, comprises 1 : 3 : 6 : 6 : 3 : 1 compounds. TABLE 1. ~~ ~ ~~ ~ Formyl conipouiids. Formnnilide [O] .......... 46" Formotoluidides. 1 ................................ 2 , ................................ 3 ................................ Fo: tilosylididcs. 1 : 2 ............................. 2 : 3 ............................. 1 : 5 ............................. 1 : 3 ............................. 2 : 4 ............................. 1 : 4 ............................. 58" liquid 52" 103'5" 68 164 113.5 76.5 116.5 Acetyl compounds. Acetnnilide [O] ............... 114" Acetotoluidides. 1 ............................... 107" 2 ................................. 65.5 3 ................................. 147 Act:toxyliclides.1 : 2 ............................ 134O 2 : 3 ............................ 99 1 : 5 ........................... 177 1 : 3 ............................. 129 2 : 4 ............................. 142'5 1 : 4 ............................ 138.5 * As a matter of couvenience, the positions in formanilide are numbered thus : NH*CHO so that positions 1 and 5 are relatively ortho to the formyl or acetyl groups respectively.CONSTANTS AND CONSTITUTION IN BENZENOIL) AMINES. 1081 TABLE 1 (continued). Formyl compounds. Forrnanilicle [0] .. . ... ... .. . 46" Formylaminot rimethylbenzenes. 1 : 3 : 5 ........................ 2 : 3 : 5 ..... ................. 120'5 1 : 2 : 4 ..................... $8 1 : 4 : 5 ........................ 1 : 2 : 3 m .. . . . . . . . . . . . . . . . . . . . . . 2 : 3 : P ............... ......... 176" 98.5 Formylan~inotetrainethylbenzenes. 1 : 2 : 3 : 4 ............... .,.... 1 : 2 : 4 : 5 ..................... 164 143.5" i : 2 : 3 : 5 ..................... 183 Formylaminopentamethylbenzene. 1 : 2 : 3 : 4 : 5 ...,........... 216.5" Acetyl compounds. Acetanilide [O] ... ,. . . . , . . . . . , 114" Acetylami no trime th yl benzenes. 1 : 3 : 5 ....................... 216'5" 2 : 3 : 5 ......... ..,........,.. 164 1 : 2 : 4 ........................ 126 1 : 4 : 5 ........................ 1 : 2 : 3 ................ * ....... 2 : 3 : 4 ........................ 164.5 ~~ Acetylaminotetrame thylbenzenes. 1 : 2 : 3 : 4 ..................... 1 : 2 : 3 : 5 ......,............. 215'5 1 : 2 : 4 : 5 .. ... .. .... ... ... ... 169" 192 Acetylaminopeiitamethy lbenzene. 1 : 2 : 3 : 4 : 5 ........,....... 215.5" The first step in the investigation was to obtain such an arrangement of these 36 melting point values that certain regularities should appear. Averages D, and D, were found for the series R. The values D, of series R are obtained by adding all the melting point values of the compounds and dividing by the number of com- pounds. The values D, by adding the highest and lowest melting points and dividing by 2. It will be observed from Table 2, firstly, TABLE 2, Compounds. I'ormxnilide . . . . . . . . . . . . . . . . . . . . . . . . . , , Formotoluidides . . . , . , . I . . . . . . . . . . . . . . . . . Formoxylidides . . .. . . . . . . . . . . . . . . . . . . . . . . Formylaniinotrimethylbenzenes . . . . . Formylaminotetramethylbenzenes . . Formylaminopentamethyl benzenes . Acetanilide.. . . . . ... . . . . . . ... .. . . . . . . . . . . . . Acetotoluidides . . . . . . . . . . . . . . . . , , , . . . . . . Acetoxylitlides . . . . . . . . . . . . . . . , . . . . . . . . . . Acetylaminotrimethylbenzenes . . .. Acctylaminotetramethylbellzenes .. Acetylaminopeiitamethylbenzenes . . 54'4 81 -6 108-8 136 163-2 190'4 47'6 81 '6 115% 149'6 183 -6 217'6 81% 108.8 136 163'2 190'4 217% 115% 136 156.5 176.8 197-2 217'6 46 107 163.7 216'5 114 106-5 136.7 192 215.5 D,. 46 116 163'2 216.5 114 106.2 138 171.2 192-2 215.51082 that the differences between D, and D, are small, and secondly, that they differ but, little from certain values, N, and N,, which are given and defined by the formulae : GORDAN AND LlMPhCH : RELATIONS BETWEEN PHYSICAL 4.6'8(p + 2) for formyl compounds.6'8(5p + 7) for formyl compounds. N,= { 4.6'S(p + 3) for acetyl N2= { 6'8(3p + 7) for acetyl ,, ,, The values of N,, N,, D,, D,, are shown in Table 2, and the differ- ences N, - N,, D, - N,, D, - N2, D, - D,, in Table 3. TABLE 3, Compounds. ~~ Formanilide.. ............................. Formotoluidides ........................ Formoxylidides ......................... Formylaminotrimethy1benze11es ..... Formylaminotetmmetliylbenzenes . Formylaminopen tamethy lbenzenes . Acetanilid e.. .............................. Acetotolnidides ........................ A cetoxylidides ..........................Acetylaminotrimethylbenxenes ..... Acetylaminotetramethylbenzenes .. Acetylaniinopentamethylbenzenes.. N2 - ivl* - 6.8 0 6'8 13 '6 20'4 27'2 34 27 '2 20'4 13'6 6-8 0 D1- NI. - 8'4 - 1.8 0.5 26 *1 - - -_ ._ 32 '4 0 -7 1.6 - 2'1 - 2'3 B1- A$. - ~ . - 1.6 - 7.9 - 19.9 - 1.1 -~ __ - 1.6 - 29.5 - 19.7 - 4.8 - 2'1 0 9 - 0.5 0 0 - 0'3 1 '3 0'2 0 The melting points of the 36 ccmpounds can be arranged in three primary classes (Table a), and the third class again can be divided into 2 sub-classes. The first class contains 6 formyl and 9 acetyl derivatives, the melt- ing points of which fall between the values N, and N,, or differ, a t most, about 2' from them. The second class comprises 2 formyl and 4 acetyl compounds, the melting points of which are more than 2 O higher than the values in N, and N,. The first of these compounds is p-acetotoluidide and all the others contain methyl groups substituted in the 1 : 5 positions.In the third class are 10 formyl and 5 acetyl compounds: their melting points are more than 2 O lower than indicated under N, and N,. Of these 15 compounds, 9 belong to the second sub-class, they contain methyl groups substituted in the 2 : 3 or 2 : 4 positions. The melting points of formyl derivatives differ more amongst them- selves than do the melting points of acetyl derivatives.CONSTANTS AND CONSTITUTIOK IN BENZENOID AMINES. 1083 Four compounds have very high melting points not differing more than 1' from 216'. TABLE 4. 1st Class. Formyl derivcbtives. [O] = 46' j [ 1 : 31 = 1 1 3.5" ; [ 1 : 41 = 1 1 6.5' ; [ 1 : 2 : 3 : 51 - 183' ; [l : 2 : 4 : 51 = 164O; [l : 2 : 3 : 4 : 51 = 216.5'.A cet y I derivatives. [O] = 114'; [I] = 107'; [1 : 21 = 134'; [l :4] = 138.5'; [2 :4] = 142.5O; [I1 : 2 : 3 : 4 : 51 = 215.5'. [Z : 3 : 51 = 164'; [2 :3: 41 = 164.5' ; [l : 2 : 4 : 51 = 192' 2nd Class. Formy! derivatives. [l : 51 = 164'; [l : 3 : 51 = 176'. 3rd Class. 1st Sub-class. liormyl derivatives. [l] = 5s' ; [2] = fluid ; [ 31 = 52' ; [l : 21 = 103.5". A cety l devivatives. [2]=65*5'; [I :3]= 129". 2nd Sub-class. Fomn yl der,ivatives. [2 : 31 = 68" ; [2 : 41 = 76.5"; [l : 2 : 41 = 9s"; [2 : 3 : 41 = 98.5'; [2 :3:5] = 120.5'; 11 : 2 : 3 :4] = 143.5'. Acetyl derivatives, [2:3]-99'; [I :2:4]=126'; [1:2:3:4]=169', As previously mentioned, 36 only of the 40 possible compounds of this class have had their melting points determined.Both the formyl- and acetyl-amino-1 : 4 : 5- and 1 : 2 : 3-trimethylbenzenes are missing.1084 PHYSICAL CONSTANTS OF BENZENOID AMINES. The melting points of these substances can be approximately calcu- lated. The differences, D, - N,, given in Table 3 are but small (with the exceptions of aniline and aminopentamethylbenzene, which give small differences D, - NJ. It may, therefore, be pretty safely assumed that for the two missing substances these numbers would also be small. On this assumption, we may take the average of D, as 136" for formylaniinotrimethyl- benzenes, and 170" for the corresponding scetyl compounds. For the formglaminotrimethylbenzenes, the average of D, may be taken as 5" higher than D,, so that D, may be about 141".I n Table 1, the lowest melting point of formylaminotrimethylbenzene is 98". The 1 : 4 : 5-modification contains the 1 : 5-arrangement, and has, probably, the highest melting point ; we have [I : 4 : 51 4- 9s" = D, = 141" and [I : 4 : 51 = 1 8 4 O . 2 The mean value of D, for the formylaminotrimethylbenzenes is 136", we have therefore : [ 1 : 3 : 5 ] + [ 2 : 3 : 5 ] + [ 1 : 2 : 4 ] + [ 1 : 4 : 5 ] + [ 1 : 2 : 3 ] + [ 2 : 3 : 4 ] = D, = 136'. Introducing the values from Table 1, 176" + 120.5" + 98" + 184" + [l : 2 : 31 + 98.5" = 1360, 6 from which we calculate for the 1 : 2 : 3-derivative the melting point 135". With the acetyl derivatives, the case is somewhat different : the one of constitution [l : 3 : 51 has the highest melting point of all, 216.5", and the 1 : 2 : 4-derivative the lowest, namely, 126".D, does not affect the melting points of the 1 : 4 : 5- and the 1 : 2 : 3-derivatives. Of these melting points, that of the 1 : 4 : 5-corn- pound is no doubt the higher, and the difference between them may be about 30". [l : 4 : 51 - [I : 2 : 31 = 30". By the formula [ 1 : 3 : 5 ] + [ 2 : 3 : 5 1 + [ 1 : 2 : 4 ] + [I : 4 : 5 ] + [ 1 : 2 : 3 ] + [ 2 : 3 : 4 ] - -- 6 D, = 170". Introducing the values from Table 1, 216~5"+164"+126"+[1 : 4 : 5 ] + [ 1 :2:3]+164*5" 6 = 170". -~ [l : 4 : 51 = 190". therefore [l : 4 : 51 + [l : 2 : 31 = 350" [1 : : 31 = 1600,ACTION OF DIASTASE AND YEAST ON STARCH-GRANULES. 1085 It will be seen from Table 1 that the melting points of the acetyl derivatives are higher than those of the correspondiug formyl com- pounds. This is more clearly shown in Table 5. TABLE 5. Constitn- tion. Aniline .......................... Tolnidine ........... ...........I 1 , , ...................... ,) ..................... Sylidine ........................ ,, ........................ ,, ........................ ,, ........................ ,, ..................... , , ...................... l i ~ ~ i i n o t ~ i ~ i i e t t ~ y l ~ ~ ~ ~ ~ ~ ~ i ~ e ... 9, ,, $ 1 , 1 Y , ,, 9 2 Y 9 9 , , 9 ... ... ... ... ... Aiiiiiiotetraiiiethylbcnze~ie 2 9 2 9 9 ) 7 ) Aminopen tnnicthyll)ei~zene 2 3 1 : 2 2 : 3 1 : 5 1 : 3 2 : 4 1 : 4 1 : 3 : 5 2 : 3 : 5 1 : 2 : 4 1 : 4 : 5 1 : 2 : 3 2 : 3 : 4 1 : 2 : 3 : 4 1 : 2 : 3 : 5 1 : 2 : 4 : 5 1 : 2 : 3 : 4 : 5 Formyl com- pound. 4 6" 58 liquid 52 103.5 68 164 113.5 76.5 116.5 176 120.5 98 184 135 98-5 143.5 183 164 216.5 Acetyl com- pound. 11 3-1 14" 107 147 134 99 177 129 142'5 138-5 216'5 164 126 190 160 164-5 169 215.5 192 215.5 65.5 67" 49 95 30 -5 31 1 3 13-5 66 22 40.5 43-5 28 6 25 66 25 -5 32.5 28 -I ERLAKGEN.