1.ApplicationNumber: US-3454348-A
1.PublishNumber: US-2558862-A
2.Date Publish: 19510703
3.Inventor: LISTON THOMAS R.
SPATZ SYDNEY M.
MAZUR RAYMOND A.
GLICK FRANCIS J.

4.Inventor Harmonized: LISTON THOMAS R()
SPATZ SYDNEY M()
MAZUR RAYMOND A()
GLICK FRANCIS J()

5.Country: US
6.Claims:

7.Description:
(en)xzE 353% @fr July '3,' 1951 1'. n. Lls'roN Erm.
DANUFACTURE 0F BROMINATEDPHTHALIC ANHYDRIDE Filed June 22, 1948 Quim Salm als@ t X933,
All
iov 023009 INVENTORS.
THOMAS R. LISTON SmNEY M.SPATZ RAYMOND A. MAZUR FRANCIS J. GLICK BY ATTORNEY.
EXONQ Patented .http 3, 195i,
assente MANUFACTURE or BnomNArEn Parme ANHYDRIDE Thomas R. Liston, Hamburg, Sydney M; Spatz,
Middletown, and Raymond A. Mazur and Francls J. Glick, Buffalo, N. Y., assignors to Allied Chemical & Dye Corporation, New York, N. Y., a corporation of New York Application June 22, 1948, Serial No.134,543
9 Claims. y(Cl. 2GB-341) This invention relates to a process for preparing brominated derivatives of phthalic anhydride and more particularly refers to a new and improved process for the production of monobromophthalic anhydride by direct bromination of phthalic anhydride.
It has been proposed according to U. S. P. 2,211,465 to effect bromination of phthalic acid byl acidifying an aqueous mixture of sodium phthalate, sodium bromide and sodium hypochlorite with hydrochloric acid. This results' inthe liberation of hydrobromic acid and hypochlorous acid, which then oxidizes the hydrobromic acid to hypobromous acid, which latter is the effective brominating agent. However, the process is involved, expensive and highly corrosive to equipment and yields chlorinated phthalic acids as contaminants, which are practically impossible to separate from the desired monobrominated phthalic acid.
The formation of undesired chlorinated phthalic acid is avoided according to U. S. P. 2,394,268 by adding bromine to an aqueous solution of a neutral salt of phthalic acid while maintaining the solution neutral by adding alkali in an amount not materially exceeding that required to neutralize the hydrobromic acid liberated in the reaction. The patent purports to obviate the use of an oxidizing agent such as sodium hypochlorite and sodium hypobromite which are required in the process disclosed in U. S. P. 2,211,465. Although these processes representthe latest developments in the art, they are cumbersome and expensive for manufacturing monobrominated phthalic acid and the corresponding anhydride.
An object of the present invention is to provide an economical, commercially practical method of producing high yields of brominated derivatives of phthalic anhydride, particularly monobrominated phthalic anhydride, by the direct bromination of phthalic anhydride.
Other objects and advantages of the present invention will be apparent from the following description and accompanying drawing.
After extensive experimentation in an attempt to brominate phthalic anhydride directly with elementary bromine in the absence of catalysts and in the resence of various agents such as antimony tr chloride, iodine, sulfur, benzoyl peroxide, powdered copper and ultraviolet light and under varying conditions of operation, we have discovered that monobrominated phthalic anhydride can be obtained in excellent yieldby a simplel inexpensive process, which comprises 2 brominating liquid phthalic anhydride with elementary bromine in the presence of a brominating catalyst comprising metallic iron or a compound containing iron. The brominated phthalic anhydride uncontaminated by chlorine compounds may be recovered from the reaction mixture by fractional distillation.
An important featureof the invention is the v direct production of brominated phthalio anhydride from elementary bromine and phthalic anhydride in the presence of a catalyst without the aid of solvents, alkali, acid, oxidizing agent or other reagents,
A speciiic embodiment of the invention comprises adding a brominating catalyst containing iron to phthalic anhydride in an amount between 1% and 10% iron by weight of the phthalic anhydride, maintaining the mixture of phthalic anhydride and brominating catalyst at a temperature in the rangeof 190'to 220 C., introducing elementary bromine in an amount from about 10% to 40% in excess over the stoichiometric amount of bromine required for monobromination of the phthalic anhydride into the mixture at a rate not materially greater than the rate at which it is consumed in the v mixture, adding finely divided Ymetallic copper to the reaction mixture thereby effecting removal of free bromine therein, and. separating monobrominated phthalic anhydride from the reaction mixture by fractionation. v
The accompanying drawing represents a diagrammatic flow sheet of one method of carrying out the present invention.
Referring to the drawing, phthalic anhydride is charged through conduit l into shell still 2 supported on furnace 3 to a level of about 1/2 to the height of vessel 2. A finely divided brominating catalyst containing iron may be admixed with the phthalic anhydride prior to introduction in shell still 2 or added through conduit 9 to the anhydride. Heat is applied to the bottom of shell still 2 by means of furnace 3 until phthalic anhydride in the vessel attains the desired`temperature preferably within the range of to 250 C. Elementary bromine is introduced through perforated pipe l into the lower portion of molten phthalic anhydride 5 contained in shell still 2 at a rate not substantially in excess of the rate at which it is consumed by phthalic anhydride. mine in vapor form together with other vaporous components pass from the top of shell still 2 through vapor release line 6 into the lower portion of reiiux column 1, which may be any Unreacted bro- 3 suitable fractionating column.' As the vapors pass upwardly to the top of reux column 1 they come in indirect heat exchangewith water flowing through cooling coil 8 thereby' condensing to form reux condensate which flows downwardly through redux column 1 and returns. by gravity through reflux leg I into, shell still 2. The fow of bromine' into the body of phthalic anhydride continues until an amount in slight excess of the theoretical amount required to form monobromophthalic anhydride is introduced. During this period of reaction the temperature of the molten phthalic anhydride is maintained within the desired range and the entire apparatus is under atmospheric pressure. Unreacted bromine and hydrogen bromide leaving the top of reflux column 1 pass through y line I2, condenserv 3, thence through line 21 and valve 28 to conventional scrubbers to trap the bromine and hydrogen bromide. To insure completion of reaction between bromine and phthalic anhydride, heating of the reaction mixture in shell still 2 is continued for about an hour or two after the discontinuance of bromine introduction into the reaction mass. copper may then be added through'conduit 9 to the reaction mixture contained in shell still Powdered more concentrated monobromophthalic anhy- 2 for the purpose of eliminating free bromine therein.
The reaction mixture is permitted to cool to a temperature of about 125 C., and a vacuum of approximately 20 mm. mercury absolutepressure is then imposed on the system by means of vacuum pump II followed by the application of heat to the bottom of shell still 2 to effect distillation of the liquid contents. The vaporous components pass upwardly through conduit 6 into fractionating column 1 and thence from the top of column 1 through line 2, condenser I3, line |4, valve 29 into receiver I5. If desired, partial cooling may be effected by cooling coil 8 at the top of .column 1 for the purpose of obtaining sharper separation of the Vaporous constituents undergoing fractionation. A continuous vacuum is maintained on the system by the suction of vacuum pump following line I6 connected to receiver I5. A scrubber 3| is desirably inserted between receiver |5 and vacuum pump II to guard the pump against product vapors. condensate accumulating in the bottom of receiver I 5 discharges through line I1 and pump |8 through line I9 into storage tank 2| or through line 22 into storage tank 23. Tanks 2| and 23 are preferably heated to keep their contents molten and capable of being withdrawn from respective'bottoms outlets 25 and 26. 'I'he first fraction distilling from shell still 2 boiling below 175 C. at 20 mm. mercury absolute pressure as measured at the top of fractionating column 1 is discharged into storage tank 2|. The next fraction boiling betweenv175 C. and 220 C. discharge into storage tank 23. The residue, that is the fraction boiling above 220 C. at 20 mm. 1 mercury absolute pressure, is withdrawn from the bottom of shell still 2 through line 24 to storage or discard. Low boiling distillate collected in storage tank 2| and consisting primarily of unreacted phthalic anhydride together with small amounts of monobromophthalic anhydride may be returned to shell still 2 as part of the charge for a subsequent operation. The inter- Liquid i drlde may be vobtained by further fractionation of this intermediate fraction, and in this event unreacted phthalic anhydride is returned to shell still 2 for further conversion. Residue discharged from still '2 through line 24 contains predominantly dlbromophthalic anhydride and other polybromophthalic anhydrides, and iron, copper and compounds of iron and of copper.
We have found that metallic iron and ferric chloride are particularly effective in -promoting the reaction between elementary bromine and phthalic anhydrideto produce monobromophthalic anhydride. Examples of other suitable iron compoundswhich may be employed in the practice of our invention are inorganic iron compounds such as ferrous and ferrie oxides, hydroxides, bromides, iodides, fluorides, sulfates, phosphates; iron salts of organic acids, e. g. ferrous and ferrie acetates, oxalates and phthalates. Iron 'salts of powerful oxidizing agents for example ferric nitrate and ferric persulfate are less preferred bromination promoters since they may also act as oxidizing agents which under the reaction conditions are sufficiently energetic to effect harmful oxidation or decomposition of phthalic anhydride or vits brominated derivatives.
Only a small amount` of ironor iron compound, for example 1% of metallic iron based on the weight of phthalic anhydride, is required tov proportion to the percentage of iron powder added as follows: 1%:20 hours; 3%=10 hours; 5%:5 hours; and l0%=3 hours.. We prefer to employ the iron 'bromination catalyst in an amount between 1% and about 10% by weight of the phthalic anhydride charge, calculated as metallic iron.. Smaller proportions of iron-catalyst produce a relatively weak stimulation of the bromination reaction and provide a progressively slower'and hence less preferred reaction. Larger amounts of catalyst, in excess of 10% iron by Weight'of phthalic anhydride, are less preferred since an inordinately large amount of additional iron catalyst is required to effect a further material reduction in time required to complete the bromination reaction. `More important, however, is the tendency by the useof such large amounts of iron catalyst to promote the formation of polybrominated derivatives of phthalic anhydride and other undesired side reactions, thereby reducing the yield of monobromophthalic anhydride and the facility and recovered from the bromination mass by fractional distillation.
mediate distillate collected in storage tank 23 is rich in monobromophthalic anhydride with relatively small amounts of unreacted phthalic anhydride and polybromophthalic anhydride. A
According to the present invention, the bromination may be performed by introducing elementary bromine into molten phthalic anhydride in which iron or an iron compound is present as a bromination catalyst. It is preferred to conduct limate. It is espciallypreferred to conduct the bromination at temperatures from about 190 C. to about 220 C., since such temperatures provide practically optimum rates of bromination with excellent mechanical operating conditions under atmospheric pressure. l
Another important factor in the operation of our process in accordance with the present invention resides in the rate of addition of bromine to the mixture of molten phthalic anhydride and iron catalyst. When a large amount of bromine is introduced at once or is permitted to accumulate in the reaction mixture, the reaction temperature is rapidly lowered by the absorption from the mixture of heat required to vaporize liquid bromine present and returned by the reiiux condenser with the consequence that the bromination reaction may be seriously retarded or even practically stopped depending on the resulting temperature in the reaction mass. Furthermore, the reiiux produced from large amounts of bromine accumulated in the reaction mixture lowers the partial pressure of phthalic anhydride thereby inducing sublimation of considerable amounts of phthalic anhydride thus tending to aggravate mechanical diiiiculties of operation.-
Although We have obtained yields of over 50% of monobromophthalic anhydride by mixing equimolecular proportions of bromine and phthalic anhydride we have found that substantially improved yields are obtained when employing a small excess of bromine, i. e. from about to about 40%, over the stoichiometric amount for monobromination. The use of an amount of bromine greater than the 40% excess increases the proportion of polybromophthalic anhydride formed at the expense of monobromophthalic anhydride and -hence is less desirable for monobromination.
Powdered metallic copper may be added at the conclusion of the bromination reaction to combine with and remove the last traces of free bromine in the mixture as Well as bromine liberated from unstable iron bromides formed, which otherwise tends to distill over and imparts color to the distillate of monobromophthalic anhydride.
After treatment with copper the mixture may be' filtered to remove the copper bromides and other solids. As a result of the copper treatment a lesscolored bromophthalic anhydride is obtained. An alternative method of removing bromine from the reaction mixture comprises passing a gas such as air through the hot bromination mass. This latter procedure is comparatively time consuming, requiring about 3 4 hours. at about 200 C. compared with less than l hour when copper is employed.
'I'he reaction mass resulting from the bromination of phthalic anhydride in accordance with tha present invention. contains predominantly monobromophthalic anhydride and minor amounts of polybromophthalic anhydride to1 gether with unreacted phthalic anhydride. In some instances this mixture may be utilized coinmercially without further separation or treatment. Generally, it is desirable to separate the monobromophthalic anhydride in substantially pure state or to produce from the reaction mass a fraction rich in monobromophthalic anhydride. Although we do not desireY to limit ourselves to any specific procedure for further treatment of the reaction mass, we have found that a fraction rich in monobromophthalic anhydride may be recovered from the bromination mixture by The traction boiling up to C. under 20 mm. of mercury absolute pressure consists largely of unreacted phthalic anhydride together with monobrominated phthalic anhydride, which constitutes as much as 10 to 15% of the theoretical yield of monobromophthalic anhydride obtained in the bromination reaction. This fraction may be subjected to further treatment for the separation of monobromophthalic anhydride from the phthalic anhydride, and the latter returned to the bromination reaction. Ordinarily, it is more convenient to reuse the fraction without further separation together with fresh phthalic anhydride in a subsequent bromination rather than try to recover its content of monobromophthalic anhydride. The fraction boiling from about 175 to 220 C. under 20 mm. mercury absolute pressure representsa product composed largely of monobromophthalic anhydride in the form of a mixture of 3- and 4bromophthalic anhydrides, together with some dibrominated derivatives of phthalic anhydride and unreacted phthalic anhydride. Technical monobromophthalic anhydride thus obtained is suitable directly for use in the manufacture of certain phthalein dyestuis employed in cosmetics. If a purer form of monobromophthalic anhydride is desired it may be obtained by further treatment of the technical product, as for example by fractionating out a relatively narrow boiling fraction from the fraction distilling between 175 to about 2207 C. Material boiling above 220 C. under 20 mm. mercury absolute pressure contains dibromophthalic anhydride as well as higher brominated derivatives of phthalic anhydride.
The following examples illustrate the inven` tion, the parts being by weight:
Example 1.-A mixture of 222 parts equivalent to 1.5 mois of technical phthalic anhydride and 11.1 parts of (iO-mesh iron powder was heated to 200-210 C. in a glass vessel provided with a reflux condenser. 320 parts equivalent to 2 mols of liquid bromine were added dropwise and portionwise during about '71/2 hours while agitating and maintaining the reaction mixture at 20D-210 C. The rate of bromine addition was controlled to avoid accumulation of bromine in the vessel as indicated by pronounced reflux of bromine or amarked lowering of the reaction texnperature. After the addition of bromine was complete the mixture was further agitated for about 2 hours at 20G-210 C`. to insure completion of the bromination reaction. 7 parts of (iO-mesh copper powder were then added and the contents of the vessel agitated for an additional 1/.3 hour. A yield of approximately 493% monobromophthalic anhydride based on the theoretical yield obtainable was produced.
A series of tests employing materials other than iron compounds were conducted in an attempt to bromin-ate phthalic anhydride with elev mentary bromine in a manner as described above. The oilowing Iagents were substituted for the iron catalyst: antimony trichloride, sulfur, benzoyl peroxide, powdered copper, and ultraviolet light. Examination of the phthalic anhydride did not occur under these conditions even when the rate of bromine addition was slowed and heating period was extended to 15 and 20 hours.
Emample 2.-240 parts equivalent to 11/2 mols of bromine .were added portionwise during l0 hours tol an agitated mixture of 222 parts equivalent to 1%; mols of phthalic anhydride and 19.5 parts of anhydrous ferric chloride in a glass ves= fractional distillation under reduced pressure. 76 sel provided with a glass reflux condenser while maintaining the'temperature o'f the reaction mixture between D-210 C. When the addition of bromine was complete the contents or the vessel were further agitated for about 1 hour at 200 to 210 C. A yield of about 60% monobromophthalic anhydride based on 'the `theoretical yield `obtainable was produced.
Example .SL-240 partsr equivalent to 11/2 mols 4of bromine were added portionwise for about 5 hours to a mixture of 222 parts equivalent to 11/2 mois of phthalic anhydride and 11.1 `parts of 60- mesh powdered iron at 200 to 210 C. The apparatus and procedure was the same as in Example 2. After the addition of bromine was complete the mixture was further agitated at 200- 210" C. for about 2 hours. A yield of about 63% monobromophthalic anhydride bas/ed on the theoretical yield obtainable was produced.
Example 4.-240 parts equivalent to 11/2 mo1sf of bromine were added portionwise during 20 hours to a mixture of 222 parts equivalent to 11/2 mois of phthalic anhydride and 2.2 parts of 60- me'sh powdered iron at a temperature at 200- 210 C. in a manner similar to that in Example 3. After the addition of bromine was complete the mixture was further agitated at 20D-210 C. for about 2 hours. A yield of approximately 67% `monobromophthalic anhydride based on the `at a rate not materially greater than the rate at which' it is consumed in the mixture and separating from the reaction products a, fraction boiling below about 175 C. at 20 mm. mercury absolute pressure and subsequently brominating said fraction in Iadmixture with additional phthalic anhydride.
2. A process for phthalic anhydride with elementary bromine to produce brominated phthalic anhydride which comprises maintaining a mixture of phthalic anhydride and a bromnating catalyst selected from the group consisting of metallic iron, inorganic iron compounds and iron salts of organic acids in an amount between 1% and 10% iron by weight of phthalic anyhdride at a temperature in `the rangeof 190-220 C., introducing elementary bromine into the mixture at a rate not materially greater than the rate at which it is consumed in the mixture, fractionating the reaction mass into a fraction boiling below about 175i C., a, fraction between about 175 C. and 220 C. and a fraction catalytically brominating 4anhydride and brominatingvv catalyst at a 8 temperatur in-the range of 190-220 C., and introducing elementary bromine in an amount from. about 10% to 40% in excess over the stoichiometric amount of bromine required for monobromination of phthalic anhydride into the mixture at a rate not materially greater than the rate at which it is consumed in the mixture.
4. A process for catalytically brominating phthalic anhydride with elementary bromine to I produce brominated phthalic anhydride which comprises adding a, brominating catalyst selected from the group consisting of metallic iron, inorganic iron compounds and iron salts of organic acids to phthalic anhydride in an amount between l% and 10% iron by weight of phthalic anhydride, maintaining the mixture of phthalic lanhydride and brominating catalyst at a temperature in the range of 190-220 C., introducing elementary bromine in an am, unt from about 10% to 40% in excess over the stoichiometric amount of bromine required for monobromination of .phthalic anhydride into the mixture at a rate not materially greater than the rate at which it is consumed in the mixture, -adding nely divided metallic copper to the reaction mixture thereby effecting removal of free bromine therein and separating a fraction rich in monobromophthalic anhydride from the reaction mixture by fractionation.
' 5. A process phthalic anhydride with elementary bromine to produce brominated phathalic anhydride which comprises adding linely divided metallic iron to phthalic anhydride in an amount between 1% and 10% iron by weight of phthalic anhydride, maintaining the mixture of phthalic anhydride and brominating catalyst at a temperature in the range of 190 C. to 220 C. and introducing elementary bromine in an amount from 10% to 40% in excess over the stoichiometric amount of bromine required for. monobromination of phthalic anhydride into the mixture at a rate not materially greater than the rate at which it is consumed in the mixture.
6. A process for catalytically brominating phthalic anhydride with elementary bromine to produce brominated phthalic anhydride which comprises adding anhydrous ferrie chloride to phthalic anhydride in an amount between 1% and 10% iron by weight of phthalic anhydride, maintaining the mixture of phthalic anhydride and brominating catalyst at s, temperature in the range of C. to 220 C. and introducing elementary bromine in an amount from 10% to 40% in excess over the stoichiometric amount of bromine required for monobromin'ation of phthalic anhydrideinto the mixture at a rate not materially greater than the rate at which it is consumed in the mixture.
7. A process for /catalytically brominating phthalic anhydride with elementary bromine to produce brominated vphthalic anhydride which comprises introducing elementary bromine into molten phthalic anhydride in the presence of a brominating catalyst selected from the group consisting of metallic iron, inorganic iron compounds and iron salts of organic acids, adding nely divided metallic copper to the reaction mixture thereby eiecting removal of free bromine therein and separating a fraction rich in monobromophthalic anhydride from the reaction mixture.
8. A process for catalytically brominating phthalic anhydride with elementary bromine to 'I5 produce brominaa phthalic anhydride which for catalytically vbrominating comprises adding finely divided metallic iron to phthalic anhydride in an amount between 1% and 10% iron by weight of phthalic anhydride, maintaining the mixture of phthalic anhydride and brominating catalyst at a temperature in the range of 190-220 C., introducing elementary bromine in an amount from about 10% to 40% in excess over the stoichiometric amount of bromine required for monobromination of phthalic anhydride into the mixture at a rate not materially greater than the rate at which it is consumed in the mixture, adding nely divided metallic copper to the reaction mixture thereby effecting removal of free bromine therein and separating a fraction rich in monobromophthalic anhydride from the reaction mixture by fractionation.
9. A process for catalytically brominating phthalic anhydride with elementary bromine to produce brominated phthalic anhydride which comprises adding anhydrous ferric chlorideV to phthalic anhydride in an amount between 1% and 10% iron by weight of phthalic anhydride, maintaining the mixture of phthalic anhydride and brominating catalyst at a temperature in the range of 190-220 C., introducing elementary bromine in an amount from about 10% to 40% in excess over the stoichiometric amount of bromine required for monobromination of phthalic anhydride into the mixture at a rate 30 not materially greater than the rate at which it is consumed in the mixture, adding :nely divided metallic copper to the reaction mixture thereby eecting removal of free bromine therein and separating a fraction rich in monobromophthalic anhydride from the reaction mixture by fractionation.
THOMAS R. LISTON. SYDNEY M. SPATZ. RAYMOND A. MAZUR. FRANCIS J. GLICK.
REFERENCES CITED 'Ihe following references are of record in the file of this patent:
UNITED STATES PATENTS OTHER REFERENCES Norris', Experimental Organic Chemistry, 1924, page 147.
Egloi, Catalysis, 1940, page 590.
Chemical Abstracts, vol. 36, 1942, page 460. Groggins, Unit Processes in Organic Synthesis. page 227.