SOLUBILITY O F SEVERAL COMPOUNDS O F THE MANNOSE SERIES I N ALCOHOLS FRED W. UPSON, EDWIN A. FLUEVOG, AND WALTER D. ALBERT Chemical Laboratory of the University of Nebraska, Lincoln, Nebraska Received April 19, 1956 INTRODUCTION
This investigation records solubilities of &rhamnose, a-d-mannose, P-d-mannose, d-mannonic-y-lactone, d-mannonic-&lactone, a-methyl-dmannoside, and d-mannitol in methyl, ethyl, allyl, propyl, isopropyl, and the four isomeric butyl alcohols. An attempt has been made to compare the solvent properties of this series of alcohols for a given sugar, and in addition t o compare the effect of structure of the sugar derivatives on solubility in a given solvent. Practically no data of this kind are now available. The results of Creighton and Klauder (4) for the solubility of mannitol in ethyl alcohol a t 60°C. do not agree with those presented here, since they report mannitol as much more soluble than we have found it to be. EXPERIMENTAL
Materials &Rhamnose hydrate was purified by recrystallization from methyl alcohol, m.p. 92"C., [a]:" = -7.7" (initial) and +8.85" (final). a-d-Mannose was obtained according to the method of Levene (6), map. 132-135"C., and P-d-mannose was obtained according to the method of Riiber and Minsaas (7). Its constants were m.p. 133.5"C.,[a]:'0= - 18" (initial) and +14.6" (final). The constants for the d-mannonic-y-lactone were m.p. 152°C. and [a]:'" = +52.3" with no change in twenty-four hours. For the ' ~ $112" two minutes after d-mannonic &lactone, m.p. 162.5"C., [ ~ r ] ~ = solution. a-Methyl-d-mannoside had a melting point of 195°C. and a rotation [a]$"= +80.6". &Mannitol melted a t 167°C. and its rotation [a]:'" = +24.5" in the presence of borax. The physical constants as above given established the purity of the different solutes used. Each of the alcohol solvent8 was purified by means of a prolonged drying process with calcium oxide and was then subjected to careful fractionation, using an efficient fractionating column. The fractions selected corresponded very closely in boiling point and density with the best values recorded in the literature. These constants are summarized in table 1. 1079
1080
F. W. UPSON, E. A. FLUEVOG, AND W. D. ALBERT
Procedure The solubility determinations were made by the synthetic method of Alexejew (1). Among the other workers who have used the method are TABLE 1 Summary of constants f o r alcohols BOILING TEMPERATURE (CORRECTEID)
ALCOHOL
Found
"C.
65.2 Methyl. . . . . . . . . . . . . . . . . . . . . . E t h y l , .. ... . . . . . . . . . . . . . . . 78.6 Allyl. . , .. . . . . . . . . . . . . . . . . . 96.4-96.6 Propyl (normal). ... . . . . . . . 97.5-97.7 82.4 Propyl (iso) ......... . . . . . . . . . 117.5 Butyl (normal). . . . . .. . . . Butyl (secondary). . . . . . . . . . . . 99.4-100.0 Butyl (iso) ....... . . . . . . . . . . . . 107.7-107.9 Butyl (tertiary)*. . . . . . . . . . . . 82.5-82.6
..
.. . . . ..
. .. . .
I
* Melting temperature
I
Accepted
DENSITY I N GRAYE PlDR CC. A T 20°C.
Found
I
Accepted
"C.
64.5 78.5 97.0 97.8 82.3 117.7 99.5 107.3 82.8
0.7916 0.7883 0.8530 0.8034 0.7853 0.8093 0.8067 0.8016 0.7810t
0.7917 0.7893 0.855 0.804 0.7854 0.810 0.808 0.802 0.781t
= 24°C.
t At 25°C.
FIG,1. THEAPPARATUS
Carrick (2), Collett and Johnston (3), Kendall and his students ( 5 ) , Schroder (8), Sidgwick and his students (9), Sunier (lo), and Ward (11). The essential feature of this method is to ascertain the temperature a t
1081
SOLUBILITY OF COMPOUNDS OF MANNOSE S E R I E S
which the last crystal just disappears when a known mixture of solvent and solute is slowly heated. Collett and Johnston (3) checked this method in comparison with the usual analytical method and found very good agreement between the two. Small glass bulbs of 3 to 15 ml. capacity similar to those described by Collett and Johnston (3) were used, and their technique was followed in filling the bulbs and obtaining the weight of solvent and solute. TABLE 2 Solubilitu i n methvl alcohol TEMPERATURE IN
"c.
MOLES OF SOLUTE PER 100 MOLES OF SOLVENT
44.8 46.1 50.1 50.2 53.9 58.9 62.6
16.7 24.4 35.5 44.0 49.9 61.4
2.18 2.29 2.83 2.84 3.38 4.22 5.07
TIMPERATURI IN
'c.
@-&Mannose
Z-Rhamnose (hydrate) 35.9 42.6 49.1 53.3 56.0 60.5
MOLES OF SOLUTE PER 100 MOLES OF SOLVENT
TEMPERATURE INOC.
41.5 45.0 51.3 55.0 59.1 64.2
II
I
40.0 47.9 53.4 60.9 67.4
0.813 1.083 1.325 1.797 2.367
a-Methyl-d-mannoside 40.2 43.7 49.8 54.9 58.4 62.4 64.6 66.8
d-Mannonic-&lactone
1.84 2.19 2.82 3.26 3.95 4.97
d-Mannonic-r-lact one
0.458 0.523 0.652 0.776 0.867 1.010 1.094 1.205
MOLES O F SOLUTB PIR 100 MOLES OF SOLVENT
35.8 45.3 50.4 54.9 56.8 63.4 66.9
II
. .
0.235 0.341 0.415 0.508 0.581 0.779 0.957
d-Mannit ol 47.0 49.7 60.8 66.0 69.7 72.9 76.6 77.3 80.5
0.0766 0.0874 0.136 0.173 0.210 0.256 0.298 0.316 0.367
Figure 1 is a rough sketch of the apparatus used. The bath was a large beaker heated by means of an electric hot plate and filled with water for temperatures up to 95°C. and with paraffin oil for higher temperatures. Two determinations were made a t one time. The bulbs were fastened to the shaker arms by means of rubber bands as indicated, and the whole was contained in a cabinet to reduce temperature variation to the minimum. The shaker arms made two hundred complete vibrations per minute; this
1082
F.
W. UPSON, E. A.
FLUEVOG, AND W. D. ALBERT
was found to produce adequate stirring of the bath. Total immersion calibrated thermometers graduated in 0.2"C. intervals were used. The temperature was raised fairly rapidly a t first and then more slowly toward the elid of a determination. The rate of heating could be controlled by the placing of one or more light bulbs in series with the heating elements. Usually approximately twenty minutes was required in raising TABLE 3 Solubility in ethyl alcohol TEMPERATURE IN " c .
MOLES OF SOLUTE PER 100 MOLES OF SOLVENT
1-Rhamnose (hydrate) 42.0 49.3 53.6 54.5 56.1 59.2 59.8 61.1 59.9
7.93 12.6 17.2 18.7 21.5 26.1 27.5
I z
a-&Mannose 43.3 52.0 57.9 58.3 61.1 67.6
0,353 0.490 0.627 0.639 0,695 0.895
6-d-Mannose 48.2 51.8 55.3 61.2 65.4 71.4
TEMPERATURE IN%.
1
MOLE0 OF SOLUTE PER 100 MOLES OF SOLVENT
d-Mannonic-?-lactone 44.1 48.3 55.9 60.4 64.5
0.207 0.250 0.357 0.427 0.519
37.9 47.4 48.5 52.4 53.9 54.6 62.0 66.1 76.2 81 .o 84.6
0.0940 0.177 0,186 0.229 0.241 0.247 0.342 0.413 0.615 0.761 0.905
TEMPERATURE INOC.
I/
I
~
~~
MOLEE OF SOLUTE PER 100 MOLES OF BOLVENT
d-Mannonic-&lactone 42.0 49.8 53.6 60.4 66.8 68.2
53.6 62.0 63.3 69.6 73.0 77.2 80.3 85.2 92.5
0.0853 0.124 0.144 0.192 0.262 0.279
.
0.0293 0.0463 0.0494 0.0634 0.0768 0.0989 0.122 0.166 0.255
0.337 0.394 0.455 0,568 0.697 0.867
the temperature the last degree. By means of the switch the shaking machine could be stopped momentarily for observation of the bulbs. The temperature recorded, as nearly as could be determined, was that point a t which the last crystal of solute just disappeared. Usually two or three determinations of the solution temperature were made with each bulb. Recrystallization was carried out as rapidly as possible by cooling the bulbs
SOLUBILITY O F COMPOUNDS OF MANNOSE SERIES
1083
in a refrigerator and shaking them by hand occasionally in order to obtain the solutes in the form of small crystals. Two careful determinations, the results of which showed a divergence not greater than 0.2"C., were considered satisfactory. The determinations with E-rhamnose were difficult because the rather concentrated solutions were cloudy, and because rhamnose has a tendency TABLE 4 Solubility in allyl alcohol TEMPERATURE IN
"c.
MOLES OF BOLUTl PER 100 POLES OF SOLVENT
I-Rhamnose (hydrate) 35.8 38.2 46.1 49.2 54.5 59.8 60.5 62.4
4.05 4.49 6.28 7.58 10.72 14.90 15.62 18,60
or-&Mannose 48.2 52.0 55.3 56.5 66.6
0.323 0.378 0.438 0.455 0.672
1 TEMPERATURD IN
"c.
MOLESOF SOLUTE PER 100 MOLES OF SOLVENT
TEMPERATURE IN
"c.
MOLES OF SOLUTE PER 100
MOLES OF SOLVENT
p-&Mannose 47.2 51.8 55.5 58.4 65.0 68.2
0.235 0.281 0.338 0.392 0.511 0,586
42.0 46.6 53.0 57.7 62.0 67.6
0.0806 0.0964 0.127 0.156 0.192 0.247
46.4 49.7 55.1 60.4 63.4
0.215 0.250 0.320 0.404 0.464
55.9 59.4 63.6 69.3 75.0 79.7 84.7
0.0296 0.0352 0.0460 0.0627 0.0854 0.112 0,141
a-Meth yl-d-mannoside 46.2 49.4 53.3 55.9 58.5 60.5 63.2 70.3
0.197 0.229 0.275 0.313 0.345 0,391 0.436 0.581
to form large crystals. The usual time required to make the determination with either of the d-mannoses was three hours. Only one determination was made with each bulb, since the CY- and P-d-mannose both undergo more or less mutarotation in alcohol solution and the recrystallized product is not a single substance. The two d-mannonic-lactones and the cr-methyld-mannoside gave no difficulties. With d-mannitol initial determinations were not reliable, since it was found to recrystallize in one of two different
1084
F. W. UPSON, E. A. FLUEVOG, AND W. D. ALBERT
TABLE 5 Solubility in n-propyl alcohol MOLES OF
IN
"c.
MOLES OFSOLVENT
I(
I
Z-Rhamnose (hydrate)
(1
@-d-Mannose
31 .O 40.0 41.3 46.1 51.2 56.5 61.1 63.2
1
I
2.43 3.32 3.61 4.43 6.04 8.04 10.33 12.44
a-d-Mannose 41.3 47.1 56.4 60.0 63.1
68.4
0.129 0.164 0.248 0.290 0.320 0.396
48.7 53.0 59.8 65.6 70.3 75.7
1
3":;55.3 64.6 68.6
MOLES OFSOLVENT
I
1
0.0849 0.105 0.158 0.244 0.296
0.077 0,099 0.148 0.194 0.270 0.386 0.622
I
MOLES OFSOLVENT
d-Mannonic-&lactone
0.123 0.149 0.192 0,250 0.306 0.419
a-Methyl-d-mannoside 45.8 48.9 54.6 60.1 68.1 75.3 86.5
11
1
45.9 50.2 53.9 59.7 65.4 71.4
0.0476 0.0566 0.0679 0.0945 0.123 0,157
67.3 73.7 78.6 89.2 90.9 97.7
0.0193 0.0236 0.0328 0.0474 0.0631 0.108 0.122 0,174
SOLUBILITY OF COMPOUNDS O F MANNOSE SERIES
1085
TABLE 6 Solubility in isopropyl alcohol TEMPERATURE IN
"c.
MOLES OF -SOLUTE PER 100 MOLES OF SOLVENT
TEMPERATUR~ IN
"c.
8-&Mannose
&Rhamnose (hydrate) 36.8 44.5 49.3 53.8 55.3 61.2
3.01 4.06 5.37 6.86 7.49 10.70
a-d-Mannose 40.2 49.3 52.3 57.7 59.3 64.2
0.131 0.191 0.227 0.297 0.321 0.388
MOLES OF SOLUTE PER 100 MOLES OF SOLVENT
47.1 51.7 58.3 62.4 67.6 71.1
(1
0.130 0.159 0.206 0.250 0.312 0.371
TEMPERATURE IN
'e.
MOLBS OF BOLUTE P E R 100 MOLES OF SOLVENT
d-Mannonic-6-lact one 45.6 51.0 55.4 61.1 65.3 69.7
0.0607 0.0748 0.0935 0.121 0.146 0.181
55.2 59.5 65.7 69.5 79.3 81.5
0.0180 0.0224 0.0318 0.0459 0.0775 0.0882
d-Mannonic-7-lactone 43.8 51.6 57.4 64.4 67.9
0.109 0.163 0.215 0.294 0.349
a-Methyl-d-mannoside 46.3 51.6 57.3 60.8 65.7 68.0 73.8 79.7
0.0876 0.129 0.164 0.206 0.254 0.276 0,362 0.486
.
1086
F. W. UI'SON,
E. A. FLUEVOG, AND W. D. ALBERT
TABLE 7 Solubilitu in n-butvl alcohol TEMPERATURE
IN
"c.
MOLES OF SOLUTE PER 100 MOLES OF SOLVENT
TEMPERATURE 1N
"c.
l-Rhamnose (hydrate) 32.3 40.9 47.6 53.6 55.2 61.0
,9-d-Mannose
1.85 2.27 3.38 4.39 4.89 6.66
41.3 51.2 55.8 60.1 65.1 72.6
a-d-Mannose
'
42.9 47.1 51.0 55.6 55.8 62.9 69.6
0.0888 0.101 0.116 0.141 0.142 0,199 0.281
MOLES O F SOLUTE PER 100 MOLES O F SOLVENT
0.0679 0,0815 0.101 0.127 0,165
0,245
TEMPERATURE IN
"c.
MOLES OF SOLUTE PER 100 MOLES O F SOLVlNT
d-Mannonic-&lac t one 48.1 50.8 53.9 59.6 65.0 69.4
0.0379 0,0414 0.0472 0.0634 0.0822 0.103
d-Mannonic-7-lactone '
47.1 51.3 54.7 60.1 63.0
71.5
I!
0,0719 0.0868 0.106 0.139 0.163 0.242
a-Me thyl-d-mannoside 45.8 56.1 56.2 62.7 67.5
73.1 91.1
0.0539 0.107 0.109 0.165 0.219 0.290 0.632
58.5 65.8 67.1 77.0 84.2 89.4 95.2
0.0131
. 0.0199 0.0207 0.0407 0.0648 0.0887 0.1337
1087
SOLUBILITY OF COMPOUNDS OF MANNOSE SERIES
TABLE 8 Solubility i n secondary-butyl alcohol MOLES OF IN
"c.
1
MOLES OF SOLVENT
11
3.25 4.04 4.53 4.68 6.41 8.74 13.86
a-&Mannose 46.1 50.8 55.4 56.4 64.0 76.1
0.132 0.162 0.199 0,209 0.281 0,438
I/
I
MOLES OF'BOLVENT
8-d-Mannose
E-Rhamnose (hydrate) 43.1 49.1 51.8 52.5 58.6 65.4 72.4
I
MOLES OF SOLVENT
45.1 48.7 53.9 58.0 65.2 70.6
1
0.0933 0.116 0.144 0.175 0.239 0.301
d-Mannonic-y-lactone 43.1 46.6 52.0 57.4 64.7 68.7
1
0.0807 0.0927 0.125 0.167 0.238 0,286
a-Methyl-d-mannoside 49.7 53.9 58.6 66.7 75.6 80.5 93.9
0.107 0.140 0.175 0.251 0.367 0.440 0.768
44.9 49.2 54.0 58.5 64.9 71.9
I1
0.0415 0.0487 0.0637 0.0827 0.115 0.152
d-Mannitol 53.5 60.3 66.1 69.5 73.0 83.3 100.8
0.0164 0.0227 0.0286 0.0356 0.0432 0.0772 0.1904
1088
F. W. UPSON, E. A. FLUEVOG, AND W. D. ALBERT
TABLE 9 Solubility in isobutyl alcohol TEMPERATURB IN
"c.
MOLES OF SOLUTE PER 100 MOLES OF SOLVENT
TEMPERATURB IN
"c.
1-Rhamnose (hydrate) 40.4 44.8 51.4 55.0 61.2 66.6
47.1 52.1 55.1 57.6 62.6 72.5
0.0848 0.102 0.118 0.135 0.180 0.269
P-d-Mannose 47.0 49.8 54.0 58.2 63.8 72.1
0.0608 0.0679 0.0820 0.103 0.137 0,203
TEMPERATURB IN
"c.
d-Mannonic-7-lactone
2.18 2.85 3.78 4.51 6.17 7.83
&-Mannose
MOLES OF SOLUTE PBR 100 MOLES OF SOLVENT
49.5 51.7 56.9 63.3 66.4 75.1
11
46.1 51.1 56.0 63.5 69.4 74.3 80.1 83.0
d-Mannonic-&lactone
0.0659 0.0770 0.102 0.142 0.164 0.236
or-Methyl-d-mannoside 0.0528 0.0746 0.104 0.154 0.221 0.285 0.363 0.420
MOLBS OF SOLUTE PER 100 MOLES OF SOLVENT
46.8 52.3 55.4 59.5 63.0 68.1
11
0.0307 0.0402 0.0461 0.0582 0,0693 0.0842
d-Mannit ol 57.5 61.3 67.4 72.1 73.6 83.3 89.5 101.8
0.0110 0.0149 0.0195 0.0269 0.0300 0,0538 0.0754 0.1636
SOLUBILITY O F COMPOUNDS O F MANNOSE S E R I E S
1089
TABLE 10 Solubilitv i n tertiary-butyl alcohol MOLES OF
MOLE8 OF
MOLES OF
OF SOLVENT
OF SOLVENT
OF SOLVENT
2-Rhamnose (hydrate) 42.4 53.2 57.1 62.3 67.4
45.3 47.3 52.8 54.2 61.6 64.2 68.7
3.97 5.99 7.10 8.72 11.40
11
P-d-Mannose
1)
d-Mannonic-&lactone
47.9 52.3 58.1 65.0 69.5 74.0
0.204 0.246 0.318 0.411 0.487 0.589
39.4 43.4 47.6 53.7 57.7 67.1
0.0638 0.0752 0.0907 0.125 0.153 0.226
35.2 41.9 48.7 55.6 59.0 70.0
0.0938 0.123 0.173 0.250 0.288 0.424
43.1 46.3 55.0 62.7 71.5 79.7 90.3
0.0203 0.0250 0.0391 0.0574 0.0845 0.1115 0.1487
38.0 41.4 55.0 60.9 71.7 83.8
0.102 0.114 0.200 0.258 0.402 0.613
0.208 0.227 0.272 0.308 0.409 0.447 0.521
75
65 55
9 45 w CY
o
3
G
4
8
iz
16
20
24
28
32
E 65
a
5
+
55
45 30 40 50 60 70 80 MOLES OF SOLUTE PER 100 MOLES OF SOLVENT
350
10
20
FIG. 2. SOLUBILITY OF I-RHAMNOSE IN ALCOHOLS Curve 1, methyl alcohol; curve 2, ethyl alcohol; curve 3, allyl alcohol; curve 4, n-propyl alcohol; curve 5, isopropyl alcohol; curve 6, n-butyl alcohol; curve 7, sec.-butyl alcohol; curve 8, isobutyl alcohol; curve 9, tert.-butyl alcohol.
CY
65
E w I--
55 45 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 MOLES OF SOLUTE PER 100 MOLES OF SOLVENT
352.0 FIG.3.
SOLUBILITY O F a-d-MANNOSE I N
1090
ALCOHOLS(SEE FIGURE 2)
i
45 ,*[ 7 6
65 55 45
75
65 55 I
0-1 I// /
45 .u' w 350
a
/I
f/
/ $4
I
I
I
I
I
I
0.3
0.4
0.5
0.6
0.7
0.8
2 9
0.2
3
65 W
a.
E 55 45
35!
FIQ. 5.
65 Ib 1.: 210 MOLES OF SOLUTE PER 100
,;.5 3!0 :.3 4!0 MOLES OF SOLVENT TEMPERATURE .*C.
SOLUBILITY O F d-MANNONIC-?-LACTONE
1091
IN
ALCOHOLS (SEE
FIQURE
2)
MOLES OF SOLUTE PER 100 MOLES FIQ.
OF SOLVENT
6. SOLUBILITY OF ~-METHYL-~-MANNOSIDE IN ALCOHOLS (SEE FIQURE 2)
0.04 0.08
I-
