Furoyl Chloride - Industrial & Engineering Chemistry (ACS Publications)

W. W. Hartman, and J. B. Dickey. Ind. Eng. Chem. , 1932, 24 (2), pp 151–152. DOI: 10.1021/ie50266a008. Publication Date: February 1932. ACS Legacy A...
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INDUSTRIAL AKD EXGINEERING CHEMISTRY

February, 1932

should be used for mercaptobenzothiazole stocks. Likewise, the lower value, 2.32 per 10" C., should be used for the crotonaldehyde-aniline condensation product. The above values have been collected in Table IV: together with the best data available in the literature. TABLEI\'.

VALUES OF TEMPERATURE COEFFICIEST

found to be 1.91 per 10" C. For crotonaldehyde-aniline, the value was 2.32 per 10" C. 2. Bssed upon combined sulfur data, the value was 2.30 (average) per 10" C., and for crotonaldehyde-aniline 2.67 per 10" C. 3. The values obtained from physical data are to be preferred for all practical purposes.

(At loo C.)

MERCAPTOCROTON- ALDERUBBER BENZOALDEHYDEHYDEAUTHORITY SULFURTHIAZOLE LITHABGE ANILINE AMMONIA .. Spence and Young (6) 2.65" Van Rossem (7)

2

0

..

..

..

..

..

..

151

ACKXO WLEDGMENT The authors are indebted to H. W. Wilson for assistance in the experimental work, and to R. P. Dinsmore for kind permission to publish the results.

2.4C

..

LITERATURE CITED

.. 2.500

Park and Maxwell Sbeppard ( 8 ) a Combined sulfur.

.. ..

2.50b

Park ( 1 )

b

.. ..

1.91b 2.30a

..

..

Physical data.

..

.. C

2.328 2.67a

.. ..

2.59c Average value

CONCLUSIONS 1. The average temperature coefficient of mercaptobenzo-

thiazole accelerated mixes, based upon physical data, was

(1) Park, IND.ENG.CHEM.,22, 1004 ( 1 9 3 0 ) . Shepard and Krall, Ibid., 14, 951 (1922). Sheppard, India Rubber World, 80, 56 (1929). Sheppard and Wiegand, [email protected].,20, 953 (1928). Spence and Young, 2. Chem. Ind. Kolloide, 11, 28 (1912). Twiss and Brazier, J. SOC.Chem. Ind., 39, 125T (1920).

(2) (3) (4) (5) (6)

(7) Pan Rossem, Comm. Netherlands Govt.Inst. Advising Rubber Trade and Rubber Ind., VI, 179-222 (1917). RECEIVED September 10, 1931. Presented before the Division of Rubber Chemistry at the 82nd Meeting of the Bmerioan Chemioal Society, Buffalo, N. Y., August 31 to September 4,1931. C. R. Park is now with the Firestone Tire and Rubber Co., Akron, Ohio.

Fu-royl Chloride W. W. HARTMAN AND J. B. DICKEY, Eustmun Kodak Co., Rochester, N . Y .

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N RECEKT years furfural (2-furaldehyde) has become

inexpensive and easily available in large quantities. The drop in price of furfural has stimulated research in the field and has produced correspondingly inexpensive derivatives, such as furoic (pyromucic) acid. Furoyl chloride1 is one of the most useful derivatives of furfural from a synthetic viewpoint because of its stability and multiplicity of reactions. Furoyl chloride was first prepared by the action of phosphorus pentachloride on furoic acid (6). Frankland and Aston ( 3 ) have reported a practically quantitative yield of furoyl chloride by treating furoic acid with about two equivalents of phosphorus pentachloride in dry chloroform in a special apparatus described by them. Baum ( I : ] and Gelissen and Van Roo11 (4) have prepared furoyl chloride by heating the acid with thionyl choride on a water bath over a period of 1 t o 2 hours. The yields were reported to be nearly quantitative. Bogert and Stull (2) using the same method, reported a yield of 79 per cent. Maxim ( 7 ) obtained a 40 per cent yield of furoyl chloride by treating the acid with thionyl chloride, and a yield of 70-80 per cent by the action of phosphorus pentachloride on the acid. Gilman and Hewlett (5) prepared the acid chloride in 75 per cent yield by treating the acid with thionyl chloride in dry benzene. An examination of the literature indicates that the yield of the acid chloride obtained by treating the acid with phosphorus pentachloride or thionyl chloride is variable. There is the possibility that decomposition is caused by impurities in the acid itself or in the reagents used. 1 Attention is called to the fact that furoyl chloride is a vigorous lachrymator and must be handled with care.

EXPERIMENTAL The preparation described here is an extension and modification of the method of Gilman and Hewlett ( 5 ) . It is believed that the method described is applicable to quantities many times that described in this report. The reaction was carried out in a 22-liter flask fitted with an inverted Liebig condenser, an S-tube, and a dropping funnel for the introduction of the thionyl chloride, and suitable means for removing the hydrogen chloride and sulfur dioxide which were evolved in the preparation. Five thousand six hundred grams (50 moles) of a commercial grade of furoic acid? were placed in the flask, and 10 liters of dry benzene3 added. The reaction mixture was then placed on a steam bath and heated to gentle refluxing, and 8294 grams (75 moles) of a commercial grade of thionyl chloride were added dropwise over a period of 4 days. The reaction mixture was not heated overnight. After the addition of the thionyl chloride, the reaction mixture was refluxed for an additional 12 hours and filtered into a 22-liter flask. The flask was fitted with a 1.5-foot (45.7-em.) fractionating column, and the benzene and excess thionyl chloride were distilled over on a steam bath. After removal of the benzene and thionyl chloride, the acid chloride was distilled from a 12-liter flask fitted with a 2.5-foot (76.2 em.) fractionating column, Liebig condenser, and water-cooled 5-liter receiver. The first fraction boiling up to 59.5" C./T mm. weighed 90-100 grams and was mostly 2 The crude acid was an air-dried material which contained 97 per cent furoic acid and about 2 per cent moisture ' T h e benzene was'dried by distilling a commerdal grade of benzene through a 1.5-foot column until the distillate was no longer milky. About 15 per cent of the benzene was distilled over

I N D U S T R I A L A N D E N G I N E E R I K G C H E M I ST R Y

152

furoyl chloride.- The-yield was 5645 grams or 89.5 per cent4 of the calculated amount of furoyl chloride boiling a t 59.561.5' C./7 mm. The 'combined fore- and after-runs weighed 130-150 grams, in addition to a residue of about 100 grams of carbonaceous material. The low- and high-boiling fractions were found to contain much furoyl chloride which could be recovered by redistillation. It was convenient to transform it to furamide by adding it to concentrated ammonia water. Thus, furoyl chloride can be prepared on a semi-commercial 4

The yield is based on the amount of furoic acid available.

Vol. 24, No. 2

scale in 89.5 per cent yield by the action of thionyl chloride on furoic acid in benzene. LITERATURE CITED (1) Baum, Ber., 37, 2949 (1904). ( 2 ) Bogert and Stull, J.Am. Chem. Soc., 48, 248 (1926). (3) Frankland and Aston, J. Chem. Soc., 79, 511 (1901). (4) Gelissen and Van Roon, Rec. frav. chim., 43, 359 (1924). (5) Gilman and Hewlett, Iowa State College J . Sci., 4, 27 (1929) (6) Lies-Bodart, Ann., 100, 325 (1856). (7) Maxim, Bul. SOC. chim. Romania, 12, 33 (1930). RECEIVEDSeptember 23, 1931.

Heat Transfer in Stream-Line Flow II. Experiments with Glycerol THOMAS BRADFORD DREW,Department of Chemical Engineering, Massachuseits Institute

oj

Technology,

Cambridge, Mass.

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T H E first paper of this fluids done were c o n s i d e r e d . NEW DA T A are reported f o r heat lransfer series (4,5 ) t h e p r e s e n t The n-butanol data, a l t h o u g h to glycerol as it jlows in dream-line motion a u t h o r , in collaboration clearly of less reliability than through a horizontal, standard '/B-inch iron-pipewith Hogan and McAdams, disthose for oil, seemed to indicate size copper tube, steam-heated over 61.75 inches cussed the then available data on a curve distinctly different from (156.8 cm.) of its lenglh. The apparatus used, heat transfer from pipe to fluid that defined by the oil data. As for the case of modified streampossible reasons for the discrepwhich is capable of unusual precision and has line flow of liquids in horizontal ancy between n-butanol and the negligible heat losses, is described in detail. round pipes. Most of the exhydrocarbon oil, differences in On a plot of (temperature rise + initial perimental work examined had Grashof number or in temperatemperature difference) us. Wc/kL, the runs b e e n c a r r i e d o u t in s t e a m ture-variation of viscosity were with a n initial temperature difference of 65" C. heated double-pipe a p p a r a t u s suggested. so that the temperature of the fall on a curfie substantially higher than do runs The need for heat-transmistube wall was, in each case, subsion studies in the region of with a n initial temperalure difference of 30" C. stantially uniform. Hence, the stream-line flow with fluids other Both curves are higher than 2he theoretical line than hydrocarbon oils, and in the r e s u l t s were p r o p e r l y com,for zero temperature difference. For a n initial turbulent range with fluids other parable with the t h e o r e t i c a l temperature difference of 65" C. the curue f o r than hydrocarbon oils, water, formula of Graetz ( 7 )and Nusselt (131 which *vresuuvoses a conglycerol lies below that for a hydrocarbon oil. and air, has long been apparent. - * stant temperature wall. It was Partlv to satisfv this need and shown that, although the theoretical equation failed consider- partly to supply additional data 0; non-isotGermal fluid fricably of representing the experimental results, the data of tion in pipes, work was started in 1930 by Harrison (8),under known reliability could be correlated with some degree of the direction of C. S. Keevi1,l to develop an apparatus that satisfaction by -the use of the dimensionless coordinates should satisfy the three following requirements: suggested by the theory-(h - t J / T - 11) and Wc/kL. In 1. It must he possible to make the necessary heat measurethe range of modified stream-line motion, for a given Wc/kL ments with substantially calorimetric precision and reproducibility. and wall temperature, the observed temperature rise was 2. Perfect operation must be possible with no more than larger than that predicted by the Graetz theory, which 1 gallon of fluid in the system so that the cost of the fluid may assumes a parabolic distribution of mass velocity. It was not limit one's choice. 3. Precise pressure-drop measurements must be possible over suggested that this effect was due to free convection currents. part of the heated length. The data at hand when the paper was written were, with the exception of a few tests on water, obtained by experimenta- During 1930-31, Botzow and Wilson ( 2 ) , continuing the work tion with hydrocarbon oils. In the two best and most com- under the direction of the author, completely rebuilt Harriplete investigations the same oil had been used. Therefore, son's apparatus and succeeded in satisfying the first two rethe authors could in no way detect with certainty possible quirements to a reasonable degree. These men were followed deviations between the results for various fluids. During in the summer of 1931 by Rynalski and Huntington (16) the discussion (4)Sherwood reported a series of experiments who, after making several noteworthy improvements in the by Kiley and Mangsen (12) on heating oil, and some work by equipment, carried out a successful series of runs using glycerol Petrie (14) on heating n-butanol. The first of these sets of as the fluid. Since these glycerol data show a distinct deviadata agreed well with the empirical curve by which the tion from the line given previously for oils, and are of an authors had represented the results of Holden (9) and of T h i t e unusually high order of reproducibility, it has seemed desirable (16), both of whom worked with a similar oil. Since Kiley t o publish them immediately and to describe the apparatus and Mangsen had used several different lengths of pipe, the with which they were obtained. agreement showed that variations in pipe length were properly 1 A t present professor of chemical engineering, Oregon State Agriaccounted for by the proposed method of plotting if similar cultural College, Corvallis, Ore .

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