AU608808B2 - Process for removing impurity - Google Patents
Process for removing impurity Download PDFInfo
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- AU608808B2 AU608808B2 AU12089/88A AU1208988A AU608808B2 AU 608808 B2 AU608808 B2 AU 608808B2 AU 12089/88 A AU12089/88 A AU 12089/88A AU 1208988 A AU1208988 A AU 1208988A AU 608808 B2 AU608808 B2 AU 608808B2
- Authority
- AU
- Australia
- Prior art keywords
- process according
- nitroaniline
- group
- containing composition
- nitrosamine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Ceased
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- 238000000034 method Methods 0.000 title claims description 45
- 239000012535 impurity Substances 0.000 title description 7
- 239000000203 mixture Substances 0.000 claims description 43
- VBEGHXKAFSLLGE-UHFFFAOYSA-N n-phenylnitramide Chemical compound [O-][N+](=O)NC1=CC=CC=C1 VBEGHXKAFSLLGE-UHFFFAOYSA-N 0.000 claims description 30
- XKLJHFLUAHKGGU-UHFFFAOYSA-N nitrous amide Chemical compound ON=N XKLJHFLUAHKGGU-UHFFFAOYSA-N 0.000 claims description 28
- 239000002952 polymeric resin Substances 0.000 claims description 13
- 229920003002 synthetic resin Polymers 0.000 claims description 13
- 125000000524 functional group Chemical group 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 8
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 7
- 239000008096 xylene Substances 0.000 claims description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 125000004397 aminosulfonyl group Chemical group NS(=O)(=O)* 0.000 claims description 5
- 150000002367 halogens Chemical class 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 5
- ZSDSQXJSNMTJDA-UHFFFAOYSA-N trifluralin Chemical compound CCCN(CCC)C1=C([N+]([O-])=O)C=C(C(F)(F)F)C=C1[N+]([O-])=O ZSDSQXJSNMTJDA-UHFFFAOYSA-N 0.000 claims description 5
- 125000000882 C2-C6 alkenyl group Chemical group 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 4
- NEKOXWSIMFDGMA-UHFFFAOYSA-N Isopropalin Chemical compound CCCN(CCC)C1=C([N+]([O-])=O)C=C(C(C)C)C=C1[N+]([O-])=O NEKOXWSIMFDGMA-UHFFFAOYSA-N 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 3
- ITVQAKZNYJEWKS-UHFFFAOYSA-N Profluralin Chemical compound [O-][N+](=O)C=1C=C(C(F)(F)F)C=C([N+]([O-])=O)C=1N(CCC)CC1CC1 ITVQAKZNYJEWKS-UHFFFAOYSA-N 0.000 claims description 3
- -1 cyano, amino- sulfonyl Chemical group 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 125000001188 haloalkyl group Chemical group 0.000 claims description 3
- UNAHYJYOSSSJHH-UHFFFAOYSA-N oryzalin Chemical compound CCCN(CCC)C1=C([N+]([O-])=O)C=C(S(N)(=O)=O)C=C1[N+]([O-])=O UNAHYJYOSSSJHH-UHFFFAOYSA-N 0.000 claims description 3
- 229920003053 polystyrene-divinylbenzene Polymers 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- UMKANAFDOQQUKE-UHFFFAOYSA-N Nitralin Chemical compound CCCN(CCC)C1=C([N+]([O-])=O)C=C(S(C)(=O)=O)C=C1[N+]([O-])=O UMKANAFDOQQUKE-UHFFFAOYSA-N 0.000 claims description 2
- 239000005587 Oryzalin Substances 0.000 claims description 2
- 125000002843 carboxylic acid group Chemical group 0.000 claims description 2
- 125000004186 cyclopropylmethyl group Chemical group [H]C([H])(*)C1([H])C([H])([H])C1([H])[H] 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 claims 1
- 150000002431 hydrogen Chemical class 0.000 claims 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-N sulfonic acid Chemical group OS(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-N 0.000 claims 1
- 229920005989 resin Polymers 0.000 description 16
- 239000011347 resin Substances 0.000 description 16
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 150000004005 nitrosamines Chemical class 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 230000002378 acidificating effect Effects 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 239000000696 magnetic material Substances 0.000 description 4
- LZGUHMNOBNWABZ-UHFFFAOYSA-N n-nitro-n-phenylnitramide Chemical compound [O-][N+](=O)N([N+]([O-])=O)C1=CC=CC=C1 LZGUHMNOBNWABZ-UHFFFAOYSA-N 0.000 description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000004009 herbicide Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 238000010626 work up procedure Methods 0.000 description 2
- IRMMUPDPGLTRFK-UHFFFAOYSA-N 1-chloro-2,3-dinitro-4-(trifluoromethyl)benzene Chemical compound [O-][N+](=O)C1=C(Cl)C=CC(C(F)(F)F)=C1[N+]([O-])=O IRMMUPDPGLTRFK-UHFFFAOYSA-N 0.000 description 1
- CGNBQYFXGQHUQP-UHFFFAOYSA-N 2,3-dinitroaniline Chemical class NC1=CC=CC([N+]([O-])=O)=C1[N+]([O-])=O CGNBQYFXGQHUQP-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 241001482237 Pica Species 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 125000004390 alkyl sulfonyl group Chemical group 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229940090961 chromium dioxide Drugs 0.000 description 1
- IAQWMWUKBQPOIY-UHFFFAOYSA-N chromium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Cr+4] IAQWMWUKBQPOIY-UHFFFAOYSA-N 0.000 description 1
- AYTAKQFHWFYBMA-UHFFFAOYSA-N chromium(IV) oxide Inorganic materials O=[Cr]=O AYTAKQFHWFYBMA-UHFFFAOYSA-N 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000006396 nitration reaction Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
1 Melb UI Melbourne hi i ~U 1348I 7 PATENTS ACT 1952-1973 COMPLETE SPECIFICATION
(ORIGINAL)
FOR OFFICE USE FE Class: MAIL 0o Int. Cl: PAl r I Application Number: t Lodged: Complete Specification-Lodged: I so Accepted: Fol 4 Published: D E D A b-O
SPATI
Priority: 2 3 FEB I8s8 S Related Art: t i AUS 1348 P/00/011 Form AM 10 L.rTO Ht FrICER SSIXTY DOLLARS SIXTY DOL TO BE COMPLETED BY APPLICANT Name of Applicant: ICI AUSTRALIA OPERATIONS PROPRIETARY LIMITED t t 44 1 tt t t r t Address of Applicant: 1 Nicholson Street GPO Box 4311 Melbourne 3001, Victoria Australia Actual Inventor: Graham BIRD John Donald WISHART Industrial Property Section Address for Service: ICI Australia Operations Proprietary Limited 1 Nicholson Street GPO Box 4311 MELBOURNE 3001 VICTORIA AUSTRALIA Complete Specification for the invention entitled: "PROCESS FOR REMOVING IMPURITY" The following statement is a full description of this invention, including the best method of performing it known to me:- "Note: The description is to be typed in double spacing, pica type face, in an area not exceeding 250 mm in depth and 160 mm in width, on tough white paper of good quality and it is to be inserted inside this form.
11710/76-L C, J, TioMpsN. Commonwelth Goernmnt Pdn~er,'Cnancrra 117 1 6 C. J i*1 AUS 1348/RLE r PROCESS FOR REMOVING IMPURITY The present inventions relates to a process for removing nitrosamines from a composition and in particular to a process of removing nitrosamines from a composition comprising at least one nitroaniline.
Many nitroanilines are important 44 biologically active compounds which are widely used ini industries.
Of particular importance are nitroaniline herbicides such as trifluralin (4-trifluoromethyl- 2,6-dinitro-N,N-di-n-propyl-aniline), isopropalin (4-isopropyl-2,6-dinitro-N,N-di-n-propylaniline), profluralin (4-trifluoromethyl-2,6-dinitro-N-propyl -N-(cyclopropylmethyl)aniline), oryzalin (4-sulfamoyl-2,6-dinitro-N,N-di-n-propyl aniline) and nitralin (4-(methylsulfonyl)-2,6-dinitro-N,Ndi-n-propylaniline).
Such nitroanilines are generally prepared by nitration of a halogenated substituted benzene
I.
2 followed by displacement of halogen with the appropriate amine, for example, by the following scheme.
F3C Cl HNO3 H3SO4 2SO4
NO
2 0 t Or 4 4 44 4 i 4 4 4 base HN(n-C 3
H
7 2 HN~n-C3H) F3C N(nC 3
H
7 2
NO
2 During the preparation of the nitroanilines, small amounts of nitrosamines are formed as an impurity, which due to their toxicity, must be removed before commercial use.
There has been a great deal of research effort to find methods of simply but effectively removing nitrosamine impurities.
For example, J. Org. Chem., Vol. 44, 784 describes a method of destroying nitrosamines using various simple acids. Acids such as sulphuric acid, hydrochloric acid and p-toluene sulfonic acid may be used to reduce the nitrosamine content of dinitroanilines.
Although such acids are effective in reducing nitrosamine levels, residual acid and decomposition product is left in the composition, often requiring 3 workup procedures involving, for example, crystallization or extraction to get rid of these acid and deccmposition residues.
We have now found that the nitrosamine level in a nitroaniline containing composition may be efficiently reduced without leaving such residues by contacting the composition with a polymeric resin comprising acidic functional groups.
Accordingly we provide a process for removing nitrosamine from a composition comprising at least one nitroaniline the process comprising contacting 0 the composition with a polymeric resin comprising functional groups selected from acidic functional groups and salts thereof.
Examples of acidic functional groups include functional groups selected from the group of carboxylic acid groups, sulfonic acid groups and phosphoric acid groups.
Preferably the polymer comprises at least one of sulfonic and phosphoric acid functional groups.
SThe most preferred acidic functional group is the S, sulfonic acid group.
The exact nature of the polymer backbone to which the acid groups are attached is not narrowly 25 critical.
The skilled artisan will be aware of a wide range of polymeric resins having the required functional groups and such resins may be adapted to be used in the process of the present invention without undue experimentation.
Suitable resins which may be used in the process of the invention include resins such as polystyrene-divinyl benzene copolymer functionalized with sulfonic acid groups.
i i -e 4 -4- Generally, the resin will be insoluble in the dinitroaniline containing compositions, although it may be advantageous in some cases that the resin be swellable in the composition thus allowing diffusion of the composition into the polymer.
It is preferred that the resin be in particulate form for ease of handing and preferably the particles of polymer will be of convenient size to allow them to be reclaimed from the process composition by filtration.
Typically, the polymer will have particle sizes in the range 20 to 5000 microns and preferably 50 to 3000 microns. However, particle sizes will of course be chosen in accordance with desired 0 15 conditions.
r The present process is carried out with the composition in the liquid phase. The liquid phase may be provided by heating a concentrated S dinitroaniline containing solid to a temperature pa 20 above its melting point. Alternatively, it may be Po convenient to carry out the process with the dinitroaniline dissolved in a solvent.
V Preferably the solvent is a non-polar solvent such as be selected from one or more of the group Ga it 25 consisting of aromatic and aliphatic hydrocarbons and halocarbons. Specific examples of such solvents 11 l include toluene, xylene, trichlorethane and chloroform.
We have found xylene to be a particularly convenient solvent.
In one embodiment of the invention a mixture of the composition and the resin is agitated, for example, using mechanical stirring. Agitation is generally continued until the desired reduction in nitrosamine level is observed.
16 19. A process according to claim 16 or claim 18 i- 5 In a further embodiment the process is carried out using a flow system wherein the nitroaniline- containing composition is passed through a particulate bed comprising particles of the resin.
This embodiment is particularly preferred in many cases as it allows the nitrosamine level to be reduced in a continuous process. This offers advantages over the batch processes known to the art, especially in large-scale manufacture of pure nitroanilines.
Examples of suitable flow systems include packed bed and fluidized bed systems.
In yet another embodiment of the invention the polymeric resin is present in a composite which S' also incorporates non-polymeric material. Preferred non-polymeric materials include magnetic materials.
Typical magnetic materials include iron; alloys of iron; chromium dioxide; magnetic ceramics; ferrites; t Q 20 and metals such as cobalt, nickel, manganese, I molybdenum and aluminum.
Preferred magnetic material is chromium r i 'dioxide. Recovery of resin incorporating magnetic material may be aided by application of a magnetic field.
6 The process may be carried out at room temperature. However, in order that the nitrosamine be removed fair:>, uickly, we have found it convenient to heat the composition, for example, to a temperature in the range 40 to 1500C. Preferably the temperature is in the range 700 to 130°C; however higher or lower temperatures and/or higher or lower pressures than atmospheric may be used if desired.
The rate at which the nitrosamine level is reduced will of course depend on a variety of factors such as temperature, concentration, nature of the resin and the desired final nitrosamine level.
Generally, the initial concentration of nitrosamine in the composition will be in the range j 10 to 1000 parts nitrosamine per million parts by weight of nitroaniline compound(s) and typically it Wo. will be desirable to reduce the nitrosamine level to j 20 within the range 0.05 to 5 parts and preferably 0.05 to 1 parts per million parts of nitroaniline. In order to reduce the nitrosamine level to such an extent process times of 10 minutes to 24 hours and preferably 10 minutes to 5 hours may be required although shorter or longer times may be used if desired.
For example, in one embodiment of the invention, the nitrosamine level of a nitroaniline composition is reduced by storing the composition over a bed of resin.
Under some conditions the nitrosamine content of a nitroaniline containing composition may actually increase on storage, and hence even after the nitrosamine level in a nitroaniline containing composition has been reduced to low level it may be advantageous to store the composition over the resin.
-7- *Preferred nitroanilines for use in the process of the invention include compounds of formula I
NO
2 2 N 1
I,"R
NO 2 wherein fit. X is independently selected from the group consisting of halogen, C 1 to C 6 alkyl, C 1 to C 6 haloalkyl, C 1 to C 6 alkoxy, C 1 to C 6 haloalkoxy, phenoxy, C 2 to C 6 alkenyl, C 2 to C 6 haloalkenyl, (C 1 to C 6 cycloalkyl)methyl, substituted phenoxy, C 2 to C 6 alkynyl, C 2 to C 6 haloalkynyl, cyano, aminosulfonyl, C 1 to C 6 alkylsulfonyl a-nd--salf-a4;y, n is form 1 to 3; and R 1and R 2are selected from hydrogen 15C1 toC6 alkyl, C 1 to C 6 cycloalkyl C 1 to C 6 halo~ty1, C. IC~ny.-1, hall I ki-l~ 1 17 b
C
1 to C 6 alkynyl, C 1 to C 6 hal alkynyl and (C 1 to C 6 cycloalkyl)methyl.
Preferred compoun of formula I include these wherein:- Xis selected om, the group consisting of halogen
C
1 to C 6 al C 1 to C 6 g haloalkyl, sulfamoyl, C 1 to 6 alkyl if onyl; 7(a)haloalkyl, C 2 to C 6 alkenyl, C 2 to C 6 haloalkenyl, C2to C 6 alkynyl, C 2to C 6haloalkynyl and (C 3toC6 cycloalkyl)methyl.
Preferred compounds of formula I include these wherein:- X is selected from the group consisting of halogen
C
1 to C 6 alkyl, C 1 to C 6 haloalkyl, sulfamoyl, C 1 to
C
6 alkylsulfonyl; n is 1; #4 0 t t t: 8 1 2 and R to R are independently selected from the group consisting of C 1 to C 6 alkyl, C 1 to C 6 haloalkyl and cyclopropylmethyl, More preferably nitroaniline is of the formula I a
NO
x2 X 2 I a NO2 wherein X is selected from the group consisting of
C
1 to C 4 alkyl, C 1 to C 4 haloalkyl, C to C4 alkynyl sulfamoyl and C 1 to C 4 AkyT sloG.I Most preferably X is trifluoromethyl and R too 0 and R 2 are n-propyl. Specific examples of compounds of formula I include the herbicides hereinbefore listed.
As hereinbefore stated, the present process generally allows nitrosamines to be removed without a chemical workup procedure to extract impurities S* 15 and/or residues. Indeed we have found that the present process provides a nitroaniline not only free of nitrosamine but also free of nitrosamine decomposition products normally produced with mineral acid decomposition procedures.
It is also an advantage of the present invention that conditions may be conveniently selected to allow the resin (and nitrosamine impurity and/or decomposition products) to be removed from the composition by a selection of physical methods.
lrl-I~,Y;~-r~cwux~-L--r I it( it I i' I rC I+ t *1 -9 For example the resin may be separated by simply decanting the nitroaniline containing composition from the catalyst or by filtering the mixture to retain the resin.
As hereinbefore discussed the flow through system is particularly suitable in large scale manufacturing operations.
The invention now demonstrated by but not limited to the following examples:- Example 1 A clean 100 L reactor was warmed to 80 0 C with hot water. The water was discharged and the reactor then charged with hot water (55 0 C 22 kg), crude chlorodinitrotrifluoromethylbenzene (37.8 kg containing 33.3 kg of active ingredient) and a water chase 12 kg). The mixture was stirred for 5 minutes at 550 then was allowed to settle.
The top aqueous layer was removed by syphoning, a warm 5% aqueous sodium carbonate solution (30 kg) was added to the reactor, the mixture was stirred for 1 minute and was then allowed to settle. The aqueous layer was again removed by syphoning.
A warm slurry comprising water (30 kg) and sodium carbonate (8.8 kg, 82% sodium carbonate) was added, the temperature was cooled to 50 0 C and di-n-propylamine (12.3 kg) was added over 1 hour.
The temperature was maintained at below 600 during the addition and at 65 30 for 2 hours thereafter.
A further 0.5 kg of the amine were added and the mixture was stirred overnight. TLC indicated that the reaction was complete.
The mixture was allowed to settle, the aqueous layer was removed and the product washed with water (30 kg).
10 "DOWEX" (trade mark) G-24 resin, a gel polystyrene- divinylbenzene copolymer functionalized with sulfonic acid group and having a parti.cle size range of approx. 400 to 1200 microns (1.5 kg) was slurried in xylene (10.5 kg) and this slurry was added to the reactor. Further xylene (21 kg) was added and the mixture was heated to 950 over minutes. Water/xylene was azeotroped and the water removed. After 2 hours the temperature had reached 135 C and the mixture was cooled.
The dry Trifluralin mixture (73 kg, 54.6% active ingredient) was examined by gas chromatography for nitrosamine.
Nitrosamine levels were found to be less than 0.5 ug/ml solution and less than 0.5 ug/g of dinitroaniline.
1 4 Example 2 The procedure of Example 1 was repeated with the following exceptions:- 32.0 g of chlorobenzene starting material was used and the quantity of other reagents was adjusted accordingly.
(ii) 1.05 molar equivalents (based on the chlorobenzene) of n-propylamine was used.
(iii) The reaction was complete after 2 hours.
(iv) The xylene solution temperature did not exceed 130 0 C. The slurry added prior to the amine comprised.
6.9 kg (0.48 molar) equivalents of sodium carbonate.
11 The yield of product solution was 71 kg and the nitrosamine levels were found to be less than 0.3 ug/ml of solution or less than 0.5 ug/g of trifluralin solid.
*C t e f r t I 44 I 41 t 4 ft C i i r .i
Claims (15)
- 2. A process according to claim 1 wherein said functional groups are selected from the group consisting of carboxylic acid groups sulphonic acid groups, phosphoric acid groups and the salts thereof.
- 3. A process according to claim 1 or claim 2 wherein said functional groups are selected from I ,osulphonic acid groups and salts thereof. II
- 4. A process according to any one of claims 1 to 3 inclusive wherein the polymeric resin comprising the functional groups is insoluble in the composition comprising at least one nitroaniline. A process according to any one of claims 1 to 4 inclusive wherein the polymer resin is in the form of particles of convenient size to allow them to be reclaimed from the composition by filtration.
- 6. A process according to any one of claims 1 to wherein the polymer resin is in the form of particles of size in the range of from 50 to 3000 microns. 13
- 7. A process according to any one of claims 1 to 6 wherein the polymer resin is a polystyrene divinyl benzene copolymer functionalized with sulfonic acid groups.
- 8. A process according to any one of claims 1 to 7 wherein the polymeric resin is contacted with a solution of the nitroaniline containing composition.
- 9. A process according to claim 8 wherein the solution comprises a solvent selected from the group I I of toluene, xylene, trichloroethane and chloroform. A process according to any one of claims 1 to 9 comprising agitating a mixture comprising the nitroaniline containing composition and polymeric resin.
- 11. A process according to any one of claims 1 to 4 v4 S.l 10 comprising passing the nitroaniline containing composition through a bed of the polymeric resin.
- 12. A process according to any one of claims 1 to wherein the nitroaniline containing composition is contacted with the polymeric resin at a temperature in the range of from 40 to 150 0 C.
- 13. A process according to any one of claims 1 to 12 wherein the initial concentration of nitrosamine in the nitroaniline containing composition is in the range of from 10 to 1000 parts by weight per million parts by weight of nitroaniline. C. 1; ~'w -1414
- 14. A process according to any one of claims 1 to 13 wherein the nitrosamine level is reduced to a level in the range of from 0.05 to 5 parts by weight nitrosamine per million parts nitroaniline. A process according to any one of claims 1 to 14 wherein the nitroaniline containing composition is maintained in contact with the polymeric resin until the nitrosamine level is in the range of from 0.05 to 5 parts by weight nitrosamine per million parts by weight nitroaniline.
- 16. A process according to any one of claims 1 to wherein the nitroaniline containing composition comprises at least one nitroaniline selected from the group consisting of the compounds of formula I NO 2 a 1 0 P n/ N R2 I (X)f 4 'NO 2 wherein 4'o,4, X is independently selected from the group consisting of halogen, C 1 to C 6 alkyl, C 1 to C 6 r haloalkyl, C 1 to C 6 alkoxy, C 1 to C 6 haloalkoxy, phenoxy, C 2 to C 6 alkenyl, C 2 to C 6 haloalkenyl, (C,3 to C 6 cycloalkyl)methyl, substituted phenoxy, C 2 to C 6 alkynyl, C 2 to C 6 haloalkynyl, cyano, amino- sulfonyl, C 1 to C 6 alkylsulfonyl and sulfamoyl. n is from 1 to 3; and I i 15 1 2 R and R are selected from hydrogen, C 1 to C 6 alkyl, C 3 to C 6 cycloalkyl, C 1 to C 6 haloalkyl, C 2 to C 6 alkenyl, C 2 to C 6 haloalkenyl, C 2 to C 6 alkynyl, C 2 to C 6 haloalkynyl and (C 3 to C 6 cycloalkyl)methyl.
- 17. A process according to any one of claims 1 to 16 wherein the nitroaniline containing composition comprises at least one nitroaniline selected from the group consisting of the compounds of formula I wherein; X is selected from the group consisting of halogen C 1 to C 6 alkyl, C 1 to C 6 haloalkyl, sulfamoyl, C 1 to C 6 alkylsulfonyl; n is 1; and 1 2 R and R are independently selected from the group C 1 to C 6 alkyl, C 1 to C 6 haloalkyl and cyclopropylmethyl. i I
- 18. A process according to claim 16 or claim 17 wherein the compound of formula I has the formula Ia N 2 R1 R X -N Ia X R 2 NO wherein X is selected from the group consisting of C 1 to C 4 alkyl, C 1 to C 4 haloalkyl, sulfamoyl and C 1 to C 4 alkylsulfonyl. Li-_ L II Lii i; i i *i i- 16
- 19. A process according wherein in the compound of selected from trifluralin, oryzalin and nitralin. A process according 19 substantially as herein to Example 1 or Example 2. DATED this 3 rd day to claim 16 or claim 18 formula I is a compound isopropalin, profluralin, to any one of claims 1 to described with reference of 1988 trt I 1( (4R a R 4 ICI AUSTRALIA OPERATIONS PROPRIETARY LIMITED BY ITS DULY AUTHORISED OFFICER Irz A RLE CRLP2.9 riL
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AU12089/88A AU608808B2 (en) | 1987-03-02 | 1987-03-02 | Process for removing impurity |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AU12089/88A AU608808B2 (en) | 1987-03-02 | 1987-03-02 | Process for removing impurity |
| AUPI0606 | 1987-03-02 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| AU1208988A AU1208988A (en) | 1988-09-01 |
| AU608808B2 true AU608808B2 (en) | 1991-04-18 |
Family
ID=3702665
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| AU12089/88A Ceased AU608808B2 (en) | 1987-03-02 | 1987-03-02 | Process for removing impurity |
Country Status (1)
| Country | Link |
|---|---|
| AU (1) | AU608808B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5196585A (en) * | 1990-10-02 | 1993-03-23 | Dowelanco | Process for treating dinitroanilines with sulfite to reduce impurities and to reduce the ability to produce nitrosamines |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU7920787A (en) * | 1986-12-30 | 1988-06-30 | Agustin Ovidio Colonna | Eliminating n,n-dipropylnitrosamine from trifluralin |
| AU593253B2 (en) * | 1985-06-06 | 1990-02-08 | Finchimica S.P.A. | An improved process for purifying crude trifluralin |
| AU594850B2 (en) * | 1987-12-29 | 1990-03-15 | Finchimica S.P.A. | A method for the treatment of dinitroanilines to reduce their nitrosamine content and/or to stabilise them against the formation of nitrosamines |
-
1987
- 1987-03-02 AU AU12089/88A patent/AU608808B2/en not_active Ceased
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU593253B2 (en) * | 1985-06-06 | 1990-02-08 | Finchimica S.P.A. | An improved process for purifying crude trifluralin |
| AU7920787A (en) * | 1986-12-30 | 1988-06-30 | Agustin Ovidio Colonna | Eliminating n,n-dipropylnitrosamine from trifluralin |
| AU594850B2 (en) * | 1987-12-29 | 1990-03-15 | Finchimica S.P.A. | A method for the treatment of dinitroanilines to reduce their nitrosamine content and/or to stabilise them against the formation of nitrosamines |
Also Published As
| Publication number | Publication date |
|---|---|
| AU1208988A (en) | 1988-09-01 |
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| MK14 | Patent ceased section 143(a) (annual fees not paid) or expired |