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T H E JOURNAL OF INDUSTRIAL A N D ENGINEERING CHEiMISTRY
operation of this plant the most efficient results were obtained with an alum dosage of 0.9 gr. per gal. and the pH of the treated water at 7.3. Larger amounts of alum, though slightly increasing the bacterial efficiency, decreased the hours of service of the filters and increased the wash water. Fluctuations in turbidity up to 195 p. p. m. were handled at pH values from 7.3 to 7.4 without difficulty. During the course of these experiments the tap water at all times conformed to the Treasury standards, even though only 0.05 to 0.18 p. p. m. chlorine was used. The last column in Table V gives the cost of treatment per million gallons, calculated on the cost of alum at $1.50 per 100 lbs. and wash water a t 3 cents per 1000 gal. Since the Treasury standards can be met, it is more economical to run the plant at a lower efficiency with less alum and more wash water. This probably would not be true if the raw water were more polluted. The data in Table V represent averages of daily results taken during thesix months prior to cleaning the sedimentation basin in February. During this time the period of sedimentation was about 4 hrs. Table VI contains similar data on the operation after the sedimentation basin was cleaned, and the period of retention was 6 hrs. These data begin with an alum treatment of 0.21 gr.per gal. and extend through 0.95 gr. per gal. Further collection of data has been stopped because of air troubles in the filters which make comparison of filter runs impossible. The data in Table VI lead us to approximately the same conclusion as that in Table V. The constancy of the composition of the Highland Park water has made it possible for these preliminary experiments
Vol. 14, No. 11
which could not have been accomplished on a river plant. The operation confirms the data in Series I on a water with constant alkalinity and variable turbidity. Confirmation of the data in Series I1 and I11 must be left to the plant handling a water with a variable alkalinity. Data on a plant using lime or soda ash would be most interesting and valuable. The subject of color removal has not been studied because the Highland Park supply does not contain color.
CONCLUSION 1-Gillespie's method for determination of pH values without the use of buffer solutions is recommended for the average waterworks laboratory. 2-Laboratory tests indicate that the amount of alum required for the coagulation of a water is dependent on the alkalinity (the buffer value of the water) and independent of turbidity. 3-Coagulation begins at a pH of 7.8, and is fairly good at 7.6 in the summer months. These values are a little lower in the winter. 4-The pH zone in which the floc is well coagulated and settles readily, lies between 7.6 and 6.6. 5-Most efficient results are obtained at the Highland Park plant when the pH of the treated water is from 7.2 to 7.3. 6-Because of the relatively good water to start with, it is more economical to run the plant at a lower efficiency with less alum and more wash water than would be used at a pH of 7.2 to 7.3.
The Preparation of Phenylglycine-0-carboxylic Acid'*'p3 I-From
Anthranilic Acid and Chloroacetic Acid By Herbert L. Haller
COLOR LABORATORY, BUREAUOF CHEMISTRY, WASHINGTON, D. c .
The following paper is a record of the study of the reaction between anthranilic acid and chloroacetic acid for the preparation of phenylglycine-o-carboxylic acid. The proper concentration in water of the reacting substances, time of reaction, ratio of anthranilic acid to chloroacetic acid, condensing agent, and temperature haue been determined. The best yields of phenylglycine-0-carboxylic acid were obtained when the following conditions were obserued: Concentration: 25 g. of anthranilic acid i n 200 CC.of water. Ratio: 2 mols of anthranilic acid t o 1 mol of chloroacetic acid. Condensing agent: 2.33 mols of sodium carbonate to 1 mal of chloroacetic acid. Temperature: 90' C . Time: 1 hu.
The use of an alkali carbonate as a condensing agent gioes a better gield of phenylglycine-o-carboxylic acid than an equiualent amount of an alkali hydroxide.
N A RECENT paper4 from this laboratory the various
I
steps involved in the so-called Heumann process for the production of indigo from naphthalene are given and the statement is made that a study of the different reactions involved in this process has been undertaken. This paper 1 Presented before the Division of Dye Chemistry at the 63rd Meeting of the American Chemical Society, Birmingham, Ala., April 3 to 7, 1922. 2 Published by permission of the Department of Agriculture. 8 Published as Contribution NQ.63 from the Color Laboratory, Bureau of Chemistry, Washington, D . C. 4 M . Phillips, THISJOURNAL, 18 ( l 9 2 l ) , 759.
deals with the preparation of phenylglycine-o-carboxylic acid from anthranilic acid by condensing it with chloroacetic acid. Two methods for preparing phenylglycine-o-carboxylic acid6 are in general use:
~,~--:kooH
1-Anthranilic acid is condensed with chloroacetic acid :
()--:-iH +
CHzClCOOH
.--f
f HCl
2-Anthranilic acid is subjected to the action of a mixture of formaldehyde and potassium cyanide: 6 Accordingto D. R. P. 111,067 thiscompound is formed when anthranilic acid is heated with glycerol or other polyhydroxy compounds and caustic alkali t o 210' to 250° C . :
U
-COOH
+
CHOH
1'
4-4KOH --+
CHzOH
U+
-COOK
+
RzCOa 2HeO -4- 8H I t can also be obtained by heating o-chlorobenzoic acid with sodium glycine to about 220° C. (D. R.P.12,546):
f NHzCHzCOONa
---f @ ~ H & o o N a
+ NaCL
oo :N :)(, For the production of large quantities of indigo these starting materials arr not abundant enough, besides being too expensive.
Nov., 1922
T H E JOURNAL OF I N D U S T R I A L A N D ENGINEERING CHEMISTRY
*
/H
*
1041
dissolved in water. The mixture is kept alkaline by further additions of caustic soda during prolonged stirring, after whiah it is partly dried, then “hydro” extracted, when the phenylglycineo-carboxylic acid is obtained as the
~
0-COOH
EXPERIMENTAL PROCEDURE
A study of the second method is planned and results will be published as soon as the experimental part has been completed. It is not known whether this method is more profitable than the alternative one using chloroacetic acid. HowI
401
I
I
I
I
I
1
I i .5
1.0
1.5
2.0
2.5
3.0
TIMEOF REACTION - HOURS Fi0.1 ever, it has recently been extensively used, especially during the war when methodss not requiring acetic acid became very important owing to the fact that supplies of acetic acid were requisitioned in all belligerent countries for the manufacture of munitions. REVIEWOF LITERATURE Phenylglycine-o-carboxylicacid was first prepared by Mauthner and Suida.7 These investigators first attempted to prepare it from o-tolylglycocoll by oxidation, but were not successful. The fusion of anthranilic acid and chloroacetic acid also failed to prodiice phenylglycine-o-carboxylicacid. Even when the fusion temperature was held below the melting point of anthranilic acid, decomposition took place with evolution of carbon dioxide. Their best results were obtained by dissolving anthranilic acid, chloroacetic acid, and sodium carbonate in water and boiling the solution for several hours. After repeated experiments, a yield of 70 to 80 per cent was obtained. According to D. R. P. 127,178, considerable quantities of anthranilodiacetic acid are formed in this procedure. The original Heumann patents states that phenylglycine-ocarboxylic acid is obtained by heating monohalogenoacetic acid and anthranilic acid, with or without water, from 1 to 2 hrs. a t about 100’ C. or over. A longer time is required for the reaction a t a lower temperature. In a later patent9 it is stated that very little anthranilodiacetic acid is formed with this procedure: but that some of the phenylglycine-o-carboxylicacid is decomposed, owing to the high temperature used in carrying out the reaction. The addition of sodium carbonate does not materially decrease the decomposition. In the last-mentioned patent, decomposition of the phenylglycine-ocarboxylic acid is prevented by the use of neutral salts of anthranilic acid and chloroacetic acid. The reaction is carried out in not too dilute solutions a t a temperature not exceeding 40 C. An acid salt of phenylglycine-o-carboxylicacid is formed, which is insoluble in the cold reaction mixture and can therefore readily be filtered off. The patent states that no anthranilodi acetic acid is formed in this procedure. According to I,evinstein,lo the conversion of anthranilic acid to phenylglycine-o-carboxylic acid is effected a t low temperatures by dissolving anthranilic acid in caustic soda, thoroughly cooling the solution, and adding the chloroacetic acid e Geotgievics and Grandmougin, “A Text-Book of Dye Chemistry,” 2nd English ed., 1920, 409. 1 Monatsh., 9 (1888), 727. 8 D . R. P. 56,273. @ D.R. P. 127,178; U. %Patent 690,326. 10 J . Soc. Dyers Colour., 17 (1901), 140.
To ascertain the most favorable conditions for the preparation of phenylglycine-0-carboxylic acid from anthranilic acid and chloroacetic acid, a study was made of the five following factors affecting the yield of phenylglycine-0-carboxylic acid: (1) Concentration in water of the reacting substances.
(2) Time of reaction.”
(3) Ratio of the reacting materials. (4) Condensing agent. (5) Temperature of the reaction mixture.
Experiments were performed in which the concentration of the reacting gubstances was made the only variable, while the time of reaction, the ratio of anthranilic acid to chloroacetic acid, and the temperature of the reaction mixture were maintained constant. Another set of experiments was conducted in which the time of reaction was the only variable factor, while the concentration of the reacting substances, the ratio of anthranilic acid to chloroacetic acid, and the temperature remained constant. From the data obtained in this manner the best conditions were deduced for time of reaction and for concentration OB the reacting substances. Experiments were then performed varying the ratio of reacting materials and employing the time and concentration found to be the most desirable. To substantiate the time of reaction factor, experiments were carried out for 1, 2, and 3 hrs. with variable ratio of anthranilic acid to chloroacetic acid and constant volume and temperature. Having thus determined the proper concentration of reacting materials, the time of reaction, and the ratio of anthranilic acid to chloroaoetic acid, conducive to maximum yield of phenylglycine-ocarboxylic acid, calculated on the basis of anthranilic acid consumed, experiments were performed in which these factors were kept constant while varying quantities of a condensing agent were added. By thus repeating the procedure outlined above it was possible to obtain data on all the factors affecting the yield of phenylglycine-0-carboxylic acid.
P
i TIMEOF REACTION - HOURS FIG.i r
11 As used throughout this paper, this term refers to the time during which the reactions were permitted t o proceed.
THE JOURNAL OF INDUSTRIAL A N D ENGINEERING CHEMISTRY
1042,
blETHoD-Twenty-five grams of anthranilic acid in a 1liter, short-neck, round-bottom flask were covered with 50 cc. less than%he total volume of water employed in the experiment, and mixed as effectively as possible by shaking the 80
so 0
4
I
i
I
I
j
I
I
/
n
/Y
,
1
,
I
Vol. 14, No. 11
144' C., and analyzed 10.10 per cent N (calcd.for C T H ~ O ~ N , N=10.22 per cent). The chloroacetic acid was a good grade and analyzed 36.9 per cent C1 (calcd. for C?H,02ClJC1= 37.52 per cent). The other chemicals were all of C. P. grade and analyzed as follows: Sodium carbonate, 99.5 per cent Na2C03; potassium carbonate, 86 per cent KzC03; sodium hydroxide, 99 per cent NaOH; potassium hydroxide, 88.3 per cent KOH. The sodium hydroxide and the potassium hydroxide were of an unusually high degree of purity. DETERMINATION OF PURITY OF PHENYLGLYCINE-O-CAR ~ O X Y L I C Acxn-The purity of the reaction product was determined by obtaining its melting point, determining the nitrogen content by the Kjeldahl method, and titrating against standard alkali.
EFFECT OF VARYING TIMEOF REACTION AND CONCENTRATION OF THE REACTING SUBSTANCES The effect of varying the time of reaction and the concentration of the reactink substances, while the temperature (b. p. of reaction mixture is loo"+ C.) of the reaction mixture and the ratio of anthranilic acid to chloroacetic acid (1mole: 1 mole) remained constant, is indicated in Table I and graphically shown in Fig. 1. In Fig. 1-4 are given the results obtained when the yield of phenylglycine-0-carboxylic acid is based on the anthranilic acid consumed in the experiment. The consumed anthranilic acid is computed as the difference between the anthranilic acid originally taken and that recovered from the mother liquor. TABLEI-EFFECT
TIMEO F REACTIONAND CONCENTRATION OF REACTINGSUBSTANCES
OF V A R Y I N G
Ratio of CsH~NHzCOOH:CHzClCOOH=1 1 (25 g.:17 2 9 . ) Temperature = Boiling point of reaction mixture ( l o o o + C.) YIELD OF PHENYI,GLYCINE0-CARBOXYLIC
2Ok
'
"/
.i
I 110
l!5
2!0
Pic
510
MOLAR RATIO:-ANTHRANILIC ACIDTO CHLORACETIC ACID FIG. 2A
3:5
,!o
flask.12 To this was added the calculated amount of chloroacetic acid13 dissolved in 50 cc. of water. The flask was heated under a reflux condenser in an oil bath to the desired temperature, the mixture being stirred by a mercury-sealed mechanical stirrer. Two thermometers,. placed in the oil bath and in the reaction mixture, respectively, recorded the temperature. Stirring was continued throughout the reaction. Upon completion of the time of reaction, the oil bath was removed, the stirring continued, and after about 10 to 15 min.14 the solution was acidified with hydrochloric acid. After standing 24 hrs. the precipitate which had formed was .filtered off and washed with water, keeping the washings separate from the mother liquor. The precipitate was dried a t 100" C. and weighed. Sodium acetate (70 g.) was dissolved in the mother liquor by stirring. After standing over night the precipitated anthranilic acid was filtered off, washed once or twice with water and dried at 100' C. This was pure anthranilic acid,l&m. p. 143" to 144"C. To the filtrate and washings about 10 g. of sodium acetate and excess saturated copper acetate solution were added. After standing for 5 to 6 hrs. the precipitated copper anthranilate was filtered off, washed once or twice with water, and dried at 100' C. MATERIALS-The anthranilic acid used was a product known as "Anthranilic Acid, Refined." It melted at 143" to 12 When a condensing agent was employed, i t was added at this point. 18 The solution was prepared by dissolving 86.1 g. of chloroacetic acid in 250 cc. of water. An aliquot part of this was diluted t o 50 cc. 14 When a condensing agent is employed, it is advantageous to cool the reaction mixture thoroughly before acidifying. Eighty per cent of the unchanged anthranilic acid can be recovered in this way.
ACID
Time Anthranilic Based on Anof ReAcid thranilic Acid EXPT. action Water Consumed Per cent Consumed, Per No. Grams Theory cent Theory Hrs. Grams cc. 1 1 500 15.4 6.42 18.1 43.6 2 2 500 13.3 8.67 24.4 45.9 3 3 15.7 8.91 500 25.0 39.8 4 16.2 10,171 1 200 28.8 63.9 5 1.5 13.7 10.80 200 55.3 30.4 13.9 10.30 200 6 2 29.0 52.3 19.9 9.00 3 7 200 39.0 25.3 13.2 11.202 1 8 100 60.0 31.5 9 2 10.63 29.9 100 17.5 42.5 7.14 10 3 21.8 20.0 100 23.0 M. p. 207' C.; found 7.04 per cent N ; calcd. for C B H O O ~ N ,= 7 IS per cent. 2 M . p 206' C , found 7.08 per cent N ; calcd. for C¶Ha04N,N-7.18 per cent.
.
The foregoing results indicate that the maximum yield of phenylglycine-o-carboxylic acid, based on the anthranilic acid consumed, is obtained when the time of reaction is 1 hr. and the concentration of the solution is 25 g. of anthranilic acid and 17.2 g. of chloroacetic acid in 200 cc. of water. It seems that at a higher concentration, while the reaction between anthranilic acid and chloroacetic acid takes place more rapidly, more of the anthranilic acid is destroyed. In the following experiments, therefore, the time of reaction was 1hr. and the concentration of the solution 25 g. of anthranilic acid in 200 cc. of water. EFFECTOF VARYINGRATIOOF ANTHRANILIC ACID TO CIILOROACETIC ACID The results of several experiments varying the ratio of anthranilic acid to chloroacetic acid while the other factors remained constant are given in Table I1 and shown graphically in Figs. 2 and 2 A . The data for Fig. 2 are based on the anthranilic acid consumed in the experiment. To substantiate the time of reaction factor, experiments were also conducted, with a variable ratio of anthranilic acid to chloroacetic acid, for different periods of time. The results are recorded in Table I1 and in Figs. 2 and 2 A .
Box., 1922
THE JOURNAL OF INDUSTRIAL A N D ENGINEERING Q!€%&SPR Y
1043
loo-
T:
P
I
1.0
MOLES OF CONDENSING AGENT FIG.3
2.0
3.0
4.0
5.0
6.0
MOLES OF CONDENSING AGENT FIG.3A
T n a m 11-EFFECT
OF VARYING RATIO O F ANTHRANILIC ACID TO CHLOROACETIC ACIDWITH VARIABLE TIMEO F REACTION 25 g. anthranilic acid used in each experiment 25 g. anthranilic acid (1 mol) : 17.2 g. chloroacetic acid (1 mol) Water = 200 cc. Temperature = Boiling point of reaction mixture (loo"+ C.)
M. p 2 0 6 ° t 0 7 0 C , found7.17 percent N,calcd for CsHo04N, N = 7 . 1 8 per cent. 2 M p 2 0 6 ' t o 7 ' C , f o u n d 7 0 0 p e r c e n t S , c a l c d forCoHsOaN,N=7 18 per cent 1
The results show that the maximum yield of phenylglycineo-carboxylic acid is obtained when a ratio of 1.5 to 2.0 mols of anthranilic acid to 1 mol of chloroacetic acid is used. The actual yield of phenylglycine-o-carboxylic acid is somewhat better when the molecular ratio of anthranilic acid to chloroacetic acid is 2 to 1. In the subsequent experiments, therefore, a ratio of 2 mols of anthranilic acid to 1 mol of chloroacetic acid was maintained.
EFFECT OF ADDING A CONDEA-SING AGENT Using the above-determined optimum conditions for concentration of anthranilic acid, time. ratio of anthranilic acid to chloroacetic acid, and with the temperature at the boiling point of the reaction mixture, experiments were performed to determine the effect of adding varying amounts of a condensing agent. Sodium and potassium carbonates and hydroxides were used. The results of several experiments are given in 'Fable 111 and graphically shown in Figs. 3 and 3 A . In Fig. 3~ results are based on the anthranilic acid consumed in the experiment.
TABLE 111-EFFECT
OF
ADDINGA CONDENSING AGENT
Ratio of CsH4NHL!OOH:CHzClCOOH=2:1 (25 g . : 8.6 g , ) Water = 200 CC. Time of reaction = 1 hr. Temperature = Boiling point of reaction mixture (looo+ C.) CONDENSING AGENT YIELD OF PHENYLGLYCINE-OMolar Ratio: CARBOXYIJC ACID Condensing Anthranilic Based on AnAgent t o Acid thranilic Acid Exm. Chloroacetic Consunied Per cent Consumed,Per NO. Grams Acid Grams Grams Theory cent Theory Sodium Cavbonaie 1 0 0 6.8 6.80 39.4 67.4 2 2.0 0.21 8.9 7.95 44.7 63.0 3 4.0 0.41 8.5 7.86 44.2 6 5 ,n 4 6.0 0.62 8.8 7.76 43.6 62.0 5 8.55 8.0 0.83 10.4 48.0 58.2 6 10.9 10.0 1.04 8.93 50.2 57.6 7 9.15 16.1 12.0 1.24 51.4 58.0 8 15.0 1.65 9.62 16.0 54.1 61.3 9 10.7 20.0 2.07 11.481 64.4 76.5 10 22.5 2.33 9.9 11.652 6 5 . 5 82.8 11 25.0 2.59 9.6 11.26 63.3 82.5 12 30.0 3.10 9.4 10.71 60.2 80.2 13 36.0 3.62 8.8 10.58 59.4 84.7 14 40.0 4.14 8.1 10.05 56.5 87.3 Potassium Carbonate 15 1n.o 0.68 9.2 8.70 49.0 67.1 20.0 1.37 10.8 16 9.83 55.3 64.2 17 25.0 1.71 10.9 10.17 57.2 65.8 30.0 2.05 10.2 11.438 18 64.3 79.2 19 40.0 2.73 11.10 9.8 62.4 79.8 20 21 22 23 24 25 26 27
Sodium Hydroxide 3.65 1.00
8.7 7.58 42.7 61.2 8.7 4.0 1,10 8.34 46.9 67.5 6.0 1.65 8.53 9.5 48.0 63.2 8.0 2.20 10.7 9.00 50.6 59.2 10.0 2.74 10.9 9.27 52.1 60.0 8.4 14.6 4.00 9.174 51.5 76.7 20.0 5.48 3.96 31 22.1 90.6 30.0 8.22 1.03 4.5 5.7 22.6 Potassium Hydroxide 5.78 1.00 28 9.1 8.58 48.2 66.0 29 10.0 8.67 1.50 8.50 47.8 60.1 30 9.9 8.52 10.00 1.73 47.9 60.7 10.5 11.56 2.00 31 9.42 53.0 62.8 32 10.6 14.45 2.50 10.15 57.0 67.4 17.35 3.00 33 10.4 55.5 9.87 63.7 34 20.00 3.45 9.8 51.4 9.14 65.3 8.3 35 23.12 4.00 51.4 9.155 77.7 24.57 4.25 6.7 36 45.5 8.10 85.2 26.01 4.50 37 7.07 6.1 39.7 81.4 38 1.52 30.00 5.19 1.9 8.6 66.3 1 M. p. 206' t o 7' C.; found 7.18 per cent N ; calcd. for CsHsOaN, N = 7.18 per cent. 2 M. p. 206" to 7' C . 4 M. p. 206' to ?: C. 3 M. p. 205' t o 6' C. 6 M. p. 204' t o o C.
It appears that when one of the alkali carbonates is employed as a condensing agent, a better yield of phenylglycineo-carboxylic acid is obtained than with an equivalent amount of one of the alkali hydroxides. This probably is caused by the much less rapid hydrolysis of the chloroacetic acid by the carbonates. Since potassium carbonate and sodium carbonate yield approximately the same results, the cheaper sodium carbonate is naturally to be preferred. On the basis
v0i. 14,N ~ ir .
THE JOURNAL OF INDUSTRIAL A N D ENGINEERING CHEMISTRY
1044
of the anthranilic acid consumed (Fig. 3A) it appears that 4 mols of sodium carbonate give the maximum yield of phenylglycine-+carboxylic acid. Fig. 3, however, shows that the maximum actual yield of acid is obtained when slightly more than 2 mols of sodium carbonate is employed, and that the
were also conducted for different periods of time at 90' C. and at the boiling point of the reaction mixture. The results of several experiments are given in Table V and graphically shown in Figs. 5 and 5 ~ .In the latter figure results are computed on the basis of the anthranilic acid consumed in the experiment. TABLEIV-EFFECT
VARYINGTHE TEMPERATURE OP TEE REACTION MIXTURE Ratio of C ~ H ~ N H Z C O O H : C H ~ C ~ C-2:l O O H(25 g.: 8.6 g.) Water = 200 .cc. Time of reaction = 1 hour Condensing agent = 22.5 g. NazCOa
EXPT.
OF
Temperature
No. O c. 1 25 2 40 3 60 4 70 5 80 6 90 7 loo+ -.., 1 M. p. 206' to 7OC. * Ad. p. 207O C. 8 M. p. 206O to 7'C.
TABLEV-EFFECT
Anthranilic Acid Consumed Grams 0 0 . 3.8 7.5 9.9 10.3 9.9
Y I E L D OF PHENYLQLYCINE-0CARBOXYLIC ACID
Grams 0 0 5.3 9.1 11.261 12.22 11.653
Based on Anthranilic Acid Per cent Consumed Per Theory cent Thkory 0 0 0 0 29.8 98.2 51.2 85.5 63.3 80.2 68.6 83.3 65.5 82.8
TIMEOF REACTION TEMPERATURE
OF VARYINQ
WITH VARIABLE
Ratio of C6H4NHzCOOH:CHzClCOOH=2:1(25 g.:8.6 g.) NazCOa = 22.5 g. Water = 200 CC. YIELD
sa50-
6 0-
EOv
700
."""+
900
formation of phenylglycine-o-carboxylicacid rapidly decreases as the amount of sodium carbonate is increased. In the following experiments, therefore, 2.33 mols (22.5 9.) of sodium carbonate were employed.
[EFFECT OF VARYING TEMPERATURE Having determined the proper concentration of anthranilic acid, time of reaction, ratio of anthranilic acid to chloroacetic acid, and condensing agent, experiments were performed at different temperatures. The results of several experiments are given in Table IV and Fig. 4. Curve 4 A gives the results when the yields are based on the anthranilic acid consumed in the experiment. 100
I
1.0
I
2.0
1 3.0
I 4.0
TIMEOF REACTION - HOURS FIG.5
I
5.0
6!0
At temperatures somewhat below the boiling point of the reaction mixture the reaction proceeds rather slowly and therefore it was thought desirable to conduct experiments for Werent periods of time at these lower temperatures. I n order to substantiate the time of reaction factor, experiments
OF
PRENYLQLYCINE-O-
CARBOXYLIC ACID Anthranilic Based on AnTemperaAcid thranilic Acid EXPT.Time t2re Consumed Per cent Consumed, Per No. Hrs. C. Grams Grams Theory centTheory 1 1 70 7.5 9.10 51.2 85.5 2 2 70 11.00 8.7 61.8 88.3 3 4 70 12.171 9.6 68.3 89.3 12.272 70 4 5 10.8 69.0 79.3 12.38 5 6 70 10.9 69.5 79.8 11.263 6 1 80 9.9 63.3 80.2 7 1.5 80 10.5 12.124 68.1 81.2 8 2 80 11.94 10.5 67.2 79.8 9 4 80 11.92 10.5 67.2 79.8 10 0.25 90 10.93 61.5 82.0 9.4 11 0.5 11.55' 90 9.5 65.0 85.4 12.208 12 1 10.3 90 68.6 83.3 11.82 13 1.5 90 9.9 66.5 84.0 11.90 14 2 90 9.8 66.9 85.5 11.97 15 4 10.5 90 67.3 80.0 11.607 16 0.5 100465.3 85.0 9.6 17 1 9.9 11.650 loo+ 65.5 82.8 11.50 18 1.5 9.6 100-k 64.7 84.3 19 2 loo+ 11.92 10.0 67.0 83.8 11.41 20 4 100464.2 80.6 10.0 1 M. p. 205' t o 6 O C. 5 M . p . 205.5' to 6 . 5 O C. 3 M. p. 203O C. 8 M.p. 207'C. 3 M. p. 206' to 7' C. 7 M.p. 206'to 7OC. 4 M. p. 206' C. 8 M . p . 206' to 7OC.
The results indicate that the maximum yield of phenylglycine-0-carboxylic acid is obtained when the reaction is conducted at 90" C. for 1 hr. This substantiates the results obtained for the time of reaction factor in the previous experiments. Approximately identical results are obtained when the reaction is conducted at 70" C. for 4 hrs. At lower temperatures the reaction proceeds too slowly to be of any practical significance. Educational programs of the various institutions offering courses in chemical engineering are to be investigated by a committee of eleven appointed by the council of the American Institute of Chemical Engineers, with a view to standardizing the training required for the degree of Ch.E. The program of the committee contemplates three years' work in obtaining the adoption of recommendations of a previous committee and the publication of a list of approved schools a t the end of this period. The committee consists of H. C. Parmalee, chairman; five representative educators: Joseph H. James, W. K. Lewis, A. H. White, R. H. McKee, and S. W. Parr; and five representative industrialists: C. E. K. Mees, A. D. Little, C. L. Reese, W. C. Geer, and W. R. Whitney.
-
An erroneous report has been circulated regarding a fire which started on the premises of A. Daigger & Co., Chicago. The fire occurred in the block in which this company is located, but no damage was done to property of the Daigger Company.
