AU594850B2 - A method for the treatment of dinitroanilines to reduce their nitrosamine content and/or to stabilise them against the formation of nitrosamines - Google Patents
A method for the treatment of dinitroanilines to reduce their nitrosamine content and/or to stabilise them against the formation of nitrosamines Download PDFInfo
- Publication number
- AU594850B2 AU594850B2 AU83110/87A AU8311087A AU594850B2 AU 594850 B2 AU594850 B2 AU 594850B2 AU 83110/87 A AU83110/87 A AU 83110/87A AU 8311087 A AU8311087 A AU 8311087A AU 594850 B2 AU594850 B2 AU 594850B2
- Authority
- AU
- Australia
- Prior art keywords
- dinitroaniline
- nitrosamines
- trifluralin
- halide
- dinitroanilines
- 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
Links
- 238000000034 method Methods 0.000 title claims description 21
- 150000004005 nitrosamines Chemical class 0.000 title claims description 19
- 238000011282 treatment Methods 0.000 title claims description 19
- XKLJHFLUAHKGGU-UHFFFAOYSA-N nitrous amide Chemical compound ON=N XKLJHFLUAHKGGU-UHFFFAOYSA-N 0.000 title claims description 16
- CGNBQYFXGQHUQP-UHFFFAOYSA-N 2,3-dinitroaniline Chemical class NC1=CC=CC([N+]([O-])=O)=C1[N+]([O-])=O CGNBQYFXGQHUQP-UHFFFAOYSA-N 0.000 title claims description 11
- 230000015572 biosynthetic process Effects 0.000 title claims description 10
- ZSDSQXJSNMTJDA-UHFFFAOYSA-N trifluralin Chemical group 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 33
- 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 claims description 12
- 230000006641 stabilisation Effects 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- BDHFUVZGWQCTTF-UHFFFAOYSA-N sulfonic acid Chemical compound OS(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-N 0.000 claims description 6
- 238000013019 agitation Methods 0.000 claims description 5
- 125000001931 aliphatic group Chemical group 0.000 claims description 4
- -1 aliphatic radicals Chemical group 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 150000005840 aryl radicals Chemical group 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 230000006378 damage Effects 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- QARBMVPHQWIHKH-UHFFFAOYSA-N methanesulfonyl chloride Chemical compound CS(Cl)(=O)=O QARBMVPHQWIHKH-UHFFFAOYSA-N 0.000 claims description 2
- 150000004820 halides Chemical class 0.000 claims 5
- HDECRAPHCDXMIJ-UHFFFAOYSA-N 2-methylbenzenesulfonyl chloride Chemical compound CC1=CC=CC=C1S(Cl)(=O)=O HDECRAPHCDXMIJ-UHFFFAOYSA-N 0.000 claims 1
- CSKNSYBAZOQPLR-UHFFFAOYSA-N benzenesulfonyl chloride Chemical compound ClS(=O)(=O)C1=CC=CC=C1 CSKNSYBAZOQPLR-UHFFFAOYSA-N 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- FRYHCSODNHYDPU-UHFFFAOYSA-N ethanesulfonyl chloride Chemical compound CCS(Cl)(=O)=O FRYHCSODNHYDPU-UHFFFAOYSA-N 0.000 claims 1
- 125000005843 halogen group Chemical group 0.000 claims 1
- KYMPISIIXXTYCL-UHFFFAOYSA-N octane;sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O.CCCCCCCC KYMPISIIXXTYCL-UHFFFAOYSA-N 0.000 claims 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 16
- 229910052742 iron Inorganic materials 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 7
- 239000011521 glass Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 230000002363 herbicidal effect Effects 0.000 description 5
- 238000000746 purification Methods 0.000 description 5
- 150000001805 chlorine compounds Chemical class 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 101150117600 msc1 gene Proteins 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical class CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 3
- XTHPWXDJESJLNJ-UHFFFAOYSA-N sulfurochloridic acid Chemical compound OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 3
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- YLKFDHTUAUWZPQ-UHFFFAOYSA-N N-Nitrosodi-n-propylamine Chemical compound CCCN(N=O)CCC YLKFDHTUAUWZPQ-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000004009 herbicide Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 230000000750 progressive effect Effects 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 230000003019 stabilising effect Effects 0.000 description 2
- GHPYJLCQYMAXGG-WCCKRBBISA-N (2R)-2-amino-3-(2-boronoethylsulfanyl)propanoic acid hydrochloride Chemical compound Cl.N[C@@H](CSCCB(O)O)C(O)=O GHPYJLCQYMAXGG-WCCKRBBISA-N 0.000 description 1
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 102100032373 Coiled-coil domain-containing protein 85B Human genes 0.000 description 1
- 101100339482 Colletotrichum orbiculare (strain 104-T / ATCC 96160 / CBS 514.97 / LARS 414 / MAFF 240422) HOG1 gene Proteins 0.000 description 1
- 101000868814 Homo sapiens Coiled-coil domain-containing protein 85B Proteins 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 101100328463 Mus musculus Cmya5 gene Proteins 0.000 description 1
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical class O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 1
- 241000613130 Tima Species 0.000 description 1
- 150000001263 acyl chlorides Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000011717 all-trans-retinol Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- RWZYAGGXGHYGMB-UHFFFAOYSA-N anthranilic acid Chemical class NC1=CC=CC=C1C(O)=O RWZYAGGXGHYGMB-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- LVTYICIALWPMFW-UHFFFAOYSA-N diisopropanolamine Chemical compound CC(O)CNCC(C)O LVTYICIALWPMFW-UHFFFAOYSA-N 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- VBEGHXKAFSLLGE-UHFFFAOYSA-N n-phenylnitramide Chemical compound [O-][N+](=O)NC1=CC=CC=C1 VBEGHXKAFSLLGE-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/82—Purification; Separation; Stabilisation; Use of additives
- C07C209/90—Stabilisation; Use of additives
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Description
P,(
AUSTRALIA
Patents Act 5 4 (XWEi'E SPECIFICATION
(ORIGINAL)
Class Int. Class Application Number: Lodged: Complete Specification Lodged: Acceptad: Published: nlis dJocunt p. *amenmcpts Made U'W Pririt setiOn 4 9 and Is correct to r lie M'llting.I APPLICANTV'S REFEfl.'CE: E018504 BENI/PR/db Name(s) of Applicant(s),* Fj~rhimica S.p.A.
Address(es) of Applicant(s): Via Porzaflo,, IManerbio (Brescia),
*ITALY.
Address for Service is: PHILLIPS 0-RflNDE jl-,1TZPATRICK Patent and Trad~e Hark AttorneyEs 367 Collins Street Melbourne 3000 AUSTRALIA Complete Specification for the invention entitled: 1)A 1 7HD FO THE TREMUT OF DINITROANILINFS TO REDUCE THEIR NITRSAMINE CThENT ANDA)R TO! STABILISE THEM AGAINST THE FORM4ATION OF
NITROSAMINES
Our Ref 79914 POF Code: 1249/64268 The following statement is a full description of this invention, including the best method of performing it known to applicant(s):, 6003q/ 1-1 1 A- I The present invention relates to a method for the treatment of nitroan'lines to reduce their nitrosamine content and/or to stabilise them against the formation of nitrosamines.
The method relates in particular to the treatment of 2, 6-dinitro-N, N-di-n-propyl-4-trifluoromethyl aniline, known under the trade name of trifluralin a compound which is widely used in agriculture as a herbicide.
ii** The presence of a nitrosamine content greater than !ppm in dinitroaniline compositions used as herbicides is considered undesirable due to the confirmed S".a carcinogenic properties of nitrosamines in animals.
0* The methods described in the technical literature for the removal of nitrosamines from crude trifluralin obtained by the synthesis method, include the treatment of the trifluralin with a concentrated aqueous solution of hydrochloric acid, or with hydrogen chloride gas (US patent No. 4,226,789) or with chlorides of inorganic acids (US patent No. 4 ,1 8 5 ,0 3 5 or with chlorine or bromine (US Patent No. 4,127,610).
It has, however, been found that even after these treatments, the di-n-propyl nitrosamine content increases during prolonged storage of the treated technical trifluralin and during subsequent industrial fusion and formulation operations for the preparation of herbicidal compositions. In particular, the increase in the nitrosamine content is encouraged by the presence of iron and is thus inevitable when trifluralin is stored in iron containers, even if they are lacquered.
WE"
S..
*SSS.
S
S
S
S
S5
S
505 _i 2 Tests carried out by the Applicant have shown a progressive increase with time in the nitrosamine content of samples of technical trifluralin stored in glass containers and in glass and iron containers, subjected to heating to a temperature of 95 0
C.
A further confirmation of the problem of the reformation of nitrosamines following heating of purified trifluralin is provided by the comparative examples in European patent application No. EP-A-126591 which relates to a method for the stabilisation of dinitroaniline compositions by the incorporation in the dinitroaniline of an addition compound of a bisulphite of ammonia or of an alkali metal and an aldehyde or a ketone.
US Patent No. 4,537,992 describes a method for the removal of the nitrosamines by subjection of the dinitroanilines to a treatment with acyl chlorides and aminobenzoates.
This method does not, however, provide any guarantee with regard to the stabilisation of the treated dinitroanilines against the reformation of nitrosamines.
German patent application No. DE-OS-333 45 157 describes a method for the production of dinitroanilines substantially free from nitrosamines and their stabilisation against the formation of nitrosamines.
The method provides for the treatment of the dinitroanilines with aromatic or aliphatic sulphonic acids, with chlorosulphonic acid or with amidosulphonic S S
S
S
3 acid.
Amongst the compounds indicated, only dodecylbenzene sulphonic acid is used commercially, this, however, being used exclusively for the stabilisation of dinitroanilines which have previously been purified of nitrosamines. In fact, since this compound is a surfactant, its presence in the higher concentration required for the purification of crude nitroaniline may give rise to the undesired formation of foams and emulsions when water is present, even in small S* quantities, in the reactor used for the treatment.
The object of the present invention is to provide a method which constitutes an overall solution both to the problem of the removal of aLtrosamines from crude trifluralin and to the problem of stabilising the purified trifluralin against the formation of nitrosamines.
For this purpose, the subject of the present invention is a method for the treatment of dinitroanilines having herbicidal action to reduce their nitrosamine content and/or to stabilise them against the formation of nitrosamines, characterised in that it comprises the steps of adding to the dinitroanilines an effective C quantity of an aliphatic or aromatic sulphonic acid having the general formula 0
NX
i i- i
J
I i mR 4 in which X is a halogen and s selected from the group consisting of linear o~ branched aliphatic radicals having from 1 to 10 carbon atoms, cycloaliphatic C5-C 6 radicals, aryl radicals and aryl radicals substituted with lower (C 1
-C
3 alkyl groups.
Although the method is generally effective as regards the stabilisation and/or purification of dinitroanilines having herbicidal action, particular reference will be made to tri. -alin in the following *fee eo** part of the present descriptic' 9 In the method according to the invention, typically 4h4.
abhov-mentioned sulphonyl chloride is added to the trifluralin in the fused state, in quantities of from 0.01 to 1% by weight with respect to the weight of the trifluralin The stabilisation is typically carried out at a temperature higher than the melting point of the trifluralin and generally within the range 70 to 100 0 C. The sulphonyl chloride is preferably added, in this case, in a ratio of from 0.01 to 0.1% by weight with agitation and the agitation is continued for a period of between 1 and 4 hours. In the case of the purification treatment carried out on crude trifluralin the treatment is effected at a temperature of between 95 and 110 C, the sulphonyl chloride being added in a ratio preferably of from 0.3 to 1% by weight. The agitation is continued fo a period of between 8 and 10 hours.
The treatment according to the invention is effective even when precursor compounds for nitrosamines, such as, di-n-propylamines, for example, are present in the trifluralin subjected to treatment.
The results obtained by means of the method acccording to the invention will be illustrated by the following examples of experimental tests.
Example 1 (Reference example) The following example illustrates the phenomenon of the formation of nitrosamines in purified trifluralin satisfying the requirements established by the EPA, that is, having a nitrosamine content of less than 0.5ppm following heating in glass containers and in the presence of glass and iron.
120g of trifluralin having a nitrosamine content
U
(NO-DIPA below) of less than 0.5ppm, obtained by means of a purification treatment carried out in the laboratory with hydrochloric acid, were placed in a glass container into which a 1Qcm 2 test piece of sheet iron was introduced. The container was then kept at a temperature of 95 C for a period of from 12 to 150 hours. A parallel control test was carried out with the use of the same quantity of trifluralin without the sheet iron test piece.
0* 0 Table I below indicates the nitrosamine contents aftir 100 and 150 hours under the above conditions, the analyses being effected with a thermal energy analyser
(TEA).
i li I i'.
7 6 TABLE I
S
~j 0* 4 000*** 00 OS S 0 05 0 9 5* 4 4**
S.
S 9 S0 S. I 5*
I
sSSps
I
000* 0 00 S 00 5 0
SO
NO-DIPA NO-DIPA NO-DIPA CONTAINER content after content after content after hours 100 hours 150 hours (ppm) (ppm) (ppm) GLASS 0.65 1.04 1.2 IRON The results in Table I confirm that the purification treatment with aqueous hydrochloric acid is not effective in stabilising the triflural2,n and that the increase in the nitrosamine content is greater when ir-on is present in the container.
Example 2 various series of technical trifluralin samples were prepared containing known quantities of di-n-propyl nitrosamine (NO-DIPA) Some of the sar--".es prepared3 also contained a known quantity of di-n-propylamine,
(DIPA).
W
4 The compositions of the prepared samples subjected to treatment are shown in Table II below.
TABLE II 0 so 00 NO-DIPA DIPA SERIES content content (ppm) (ppm) A 0.24 B 1.93 C D 0.24 2 E 0.24 F 1.97 2 G 1.97 H 2.51 1 9.2 0 of technical trifluralin were placed in a glass container into which a 10 cm 2 teat piece of sheet iron was introduced and to ,which a known quantity of -a A3iph a tic or .,romatic acid selected from the above-mentioned group was added. The 8 container was tien kept at a temperature of 95 C for a period of from 12 to 160 hours.
A parallel control test was carried out for each sample, with the use of the same quantity of trifluralin but without the addition of the treatment additive. Samples were taken after 12, 48, 96, 150 and 160 hours and, in each case, their NO-DIPA contents were determined by TEA.
The results of the tests are shown in the following tables, see** e s S go *l -Llr lL .L i i iL41 i 4> Ii .uji
C
e.g.
ggSgg~ 0 6 *0 @6 0
C
g'~ S 0 Og go
C
C..
C.
S C
CO
OC U
C.
CO
C
0 CC S CS
S
*0o~ C *0
C.
ge S E Rl I ES A lquantity of NO-DIPA (ppm) at various; t im-±s AD D IT IV E 12 h 4,9h196h 1-50 h MMIRN SULPiVIINL 0.1 0.05 0.05 0 05 A s.
QULOPJDE
OCTNNIE SI)LPUGKYL 0.1 0.05 0.05 0.05 Abs.
BENZENE SLJLPHGNYL 0.1 0,05 0,05 0 05 Abs., Cl LRID)E COW MNL 0.87 1,41 1.231 1.,41 2~ *00 0 0 00 00 S ER IES 13 quantity of NO-DIPA (ppm) at various tijhu-s ADD IT IV J% 12h 148_hJ 96h __150 1 ME~TIAI\1E SULPIMYT, 0.1 0,05 0.05 0,05 Abs.
OCrANF StILPIIONY\YT., 0.1 0.17 0.05 0.05 Abs.
CHLORIDE
BEI1ZENE St)LPUONYL 0.1 1.61. 0. 33 0,05 Abs.
ILORIDr CohN\rFo1. 2,6 2.56 2.8 2,53 S E H~ .1 E S C qluantity of NO-E)IPA (PPM) at variwxs t iiin--s A D D IT I VE 12 h 148 r 96 h 150I MEINANE SULPUONYL 0.1 Q.38 0.05 00 0Cf[LORIDE OCAN ULHNYJ0.1 0,05 0.05 0,05 B3ENZENE SULI:?110NYL 0,1 0,7 0.05 0,05 CO~'TUL 43,84 4.87 5.52 S E R I E S D quantity of NO-DIPA (PPM) at various timas A DD IT I V F 12 h 48 h 196h 10 lSh EIANE SUTLIIONYL 0.1 0.06 0.05 0.05 TUMI.4 .SULIIQNYL, 0,107 0, 05 (I I w RI D P 4
I
L-
0000 0 o 0060 *0 a0 00 a I *0 go
S
*i S i S 9* 00 0 06 S *i *i S E R I ES E quantity of NO-DIPA (ppm) at various tiiies A D D IT I V E 12 h 48 h 96 h 150 h L17IANEL SULPHOYIIO 0.1 0.07 0.05 0,05 Q ILOIDE BENDZFIE SULPHONTYL 0.1 0.83 0.05 0.05
CIILORIDF
CONTRL 1.3j 1.82 2.91 S E R I ES F quantity of PO-DIPA (ppm) at varims tb.Cs ADD IT I VE J 12 h 48 h 96 hI 2O OGPPNF SULPHONYL 0.1 0,74 f0.44 pI'LJEN SUPHONL 0.1 0.2i33 0.05 0 .05 i
UTLORIDE
cOtrlNL 2.76 2,$6 3.71{ S E R I qu G latity Of NO-UIPA (pm) at various tims A D DITI V %5 12 h 48 h 96h 1_50 h, t'ANE SULLIJONYL 0,1 0.05 0.05 0,05 QCl RIDE p.'TQWE*N SnVINYL 041 2.17 2.1 1,43 2,54 3i81 4,15 :I I e.g.
0 000000 0 6 *0*006 0 0* 60 0
SS
0 0
S.
OS
S
@OS
0* S 0 .0 00 S
OS
o so
S
0060SS
S
@000 0* 00 0 00 0 00
S.
SERIE S H QUANTITY OF 140-DIPA AT VARIOUS TIM S ADDITIVE 12h 48h 96h 160h 'ETHMAF "-ULPIIONYI, C.1WPJRDE 0.02 2.2 1.68 1.37 0,4 BI-NZFN, SUJLPIIONYL, GIOID 0.02 1.56 0,64 0,24 0,15 CONTFCL 2.4 2.57 2.85 2,52 QUANPTY OF NO-DIPA SERIES I AT VA1RIMXS TINIFS ADDITIV E 1% 121h 46h 95h IGQh
K
1 It!Ni S-bTpONy't, ~HQI~ Q.02 5.72 0, 29 0,24 0.22 10o66 11 85 12,0Z 10,68 777 000i g i 0 *«0 .4
S*
S S*
S
0@ 13 The experimental tests reported in the tables clearly indicate, not only the stabilisation of the nitrosamine content, but above all a progressive reduction thereof with time, even after prolonged heat treatment. The effectiveness of the sulphochlorides according to the invention in the stabilisation and reduction occurs both with parified trifuralin thac is having a nitrosamine content which satisfies the EPA standards, and with technical trifluralin having a nitrosamine content greater than 0.5ppm. The sulphochlorides according to the invention are, furthermore, effective when added in concentrations of only 0.02% by weight with respect to the trifluralin and even when di-n-propylamine (DxL)A) which, as is known, is thought to be a precursor of nitrosamines, is present in the trifluralin It follows, therefore, that the additives according to the invention are able to display their action both at the stage of commercial formulation of herbicidal compositions including trifluralin and in the treatment of technical trifluralin obtained by synthesis.
Example 3 Destruction of ni.rosodipropyla'" ine in trifluralin with chlorides of sulpho' ic acids.
crude On the basiF of the positive results obtained in the stabilisation tests, the possibility of using chlorides of sulphonic acids as nitrosamine destroyers was also checked. For this purpose, a series of tests was carried out with the use of samples of trifluralin having NO-DIPA contents in the range 60 tp 350ppm and aulphonic acid chlorides in quantities of between 0.3 and 1% with respect to the crude trifluralin at I I I JL L 14 temperatures of between 95 and 110 C, for periods of 8-10 hours.
Te-t i.
500g of crude trifluralin having an initial NO-DIPA content of 119ppm, were introduced into a 1 litre flask provided with an agitator, and to this were added 2.5g of methane sulphonylchloride, equal to by weight of the crude trifluralin The mixture was *se heated to 95 C for 8 hours with rapid agitation. A sample was then taken and analysed by TEA and a NO-DEPA content of 0.07ppm was found.
o The following table summarises the conditions and results of the tests carried out.
SO
SO
s **so o S* 0 6
-I
L
@09a 6 S 65600: 6 a D a6 sO *r 0
S.
S S
S
INITIAL FINAL 1%to TEIPERATURR 'r'IME NO-DIPA NO-DIPA 2 trifluraline .Io) (IlOURS) (ppm) (ppln) 350 ABSENT BSCi 1 95 8 20 350 ABSENT MSC1 1 95 8 30 110 0.06 MSC1 1 95 8 40 110 0.25 0501 1 95 8 50 350 ABSENT riSCi 0.5 95 8 G 0 119 0.07 SC1 0.5 95 8 60 0,15 MSC1 0.5 95 8 60 0,3 BSC1 0.5 105 8 90 101 0.18 NSC1i 0.5 100 100 le5 0.35 OSC1 0.5 100 110 125 0.15 OSCI 0,5 95 120 110 0.31 BSC1 0.3 105 130 60 0.28 OSCi 0.3 110 140 350 0,22 MsC1 0,3 150 138 0118 MSC1 0,3 95 8 S U
S.
a 5506 q *0 I BSC1 0SC1 scl BENZENE StPIHOMTfRIDE OCrANE 'SULPHIOQ ILORIDE MpmI lN SULPI OCULO1DE 16 In all the tests carried out, the t-erm "absent" relates to the NO-DIPA content and should be understood to mean that the nitrosamine content was less than the lower threshold liimit of the TEA instrument.
In all the tests carried out the final NO-DIPA content, after treatmient for 8-10 hours, was less than the limit of 0.5ppm required by the standards.
41a so..
0..0.
Claims (6)
1. A method for the treatment of dinitroanilines to reduce their nitrosamine content and/or to stabilise them against the formation of nitrosamines, comprising the steps of adding to the dinitroaniline compositions a quantity of an halide of an aliphatic or aromatic sulphonic acid of between 0.01 and 1% by weight of the dinitroaniline to the dinitroaniline in the fused state with agitation, said halide of an aliphatic or aromatic sulphonic acid having the Jo general formula: off* 0S 0e *00 0 *5 S S a 0S 99*99: 0 as S 0e S S0* S* 0 i X S R II where X is a halogen and R is selected from the group consisting of aliphatic radicals having from 1 to 10 carbon atoms, cycloaliphatic C 5 -C 6 radicals, aryl radicals and aryl radicals substituted with CI-C 3 alkyl groups.
2. A method according to Claim 1 for the stabilisation of technical-quality dinitroanilines against the formation of nitrosamines, in which the halide of a sulphonic acid is added to the technical dinitroaniline in quantities of from 0.01 to 0.1% by weight with respect to the dinitroaniline.
3. A method according to Claim 1 for the destruction of nitrosamines in crude dinitroaniline, in which the halide of a sulphonic acid is added to the crude dinitroaniline at a temperature of from 95 to 110 0 C, in quantities of from 0.3 to 1% by weight with respect to the dinitroaniline.
4. A method according to any one of Claims 1 to 3, in which the halide of a sulphonic acid is selected from the group consisting of methane sulphonyl chloride, ethane sulphonyl chloride, octane sulphonyl chloride, benzene sulphonyl chloride, and toluene sulphonyl chloride.
A method according to any one of Claims 1 to 4 in which the dinitroaniline is trifluralin. i 18
6. A method according to Claim 1 substantially as hereinbefore described with reference to Examples 2 and 3. DATED: 14 November, 1989 FINCHIMICA S.p.A. By their Patent Attornaeys: PHILLIPS ORMONDE FITZPATRICK 0 00 0*e 0 0 0
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AU83110/87A AU594850B2 (en) | 1987-12-29 | 1987-12-29 | A method for the treatment of dinitroanilines to reduce their nitrosamine content and/or to stabilise them against the formation of nitrosamines |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AU83110/87A AU594850B2 (en) | 1987-12-29 | 1987-12-29 | A method for the treatment of dinitroanilines to reduce their nitrosamine content and/or to stabilise them against the formation of nitrosamines |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| AU8311087A AU8311087A (en) | 1989-07-06 |
| AU594850B2 true AU594850B2 (en) | 1990-03-15 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| AU83110/87A Ceased AU594850B2 (en) | 1987-12-29 | 1987-12-29 | A method for the treatment of dinitroanilines to reduce their nitrosamine content and/or to stabilise them against the formation of nitrosamines |
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| Country | Link |
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| AU (1) | AU594850B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU608808B2 (en) * | 1987-03-02 | 1991-04-18 | Ici Australia Operations Proprietary Limited | Process for removing impurity |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU3945278A (en) * | 1977-09-02 | 1980-03-06 | Eli Lilly And Company | Dinitroaniline purification |
| AU3665384A (en) * | 1983-12-14 | 1985-06-20 | Industria Prodotti Chimici S.P.A. | Processes for the preparation of nitrosamine-free N, N-disubstituted nitroaromatic amines and for the stabilization of these compounds against the formation of nitrosamines |
-
1987
- 1987-12-29 AU AU83110/87A patent/AU594850B2/en not_active Ceased
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU3945278A (en) * | 1977-09-02 | 1980-03-06 | Eli Lilly And Company | Dinitroaniline purification |
| AU3665384A (en) * | 1983-12-14 | 1985-06-20 | Industria Prodotti Chimici S.P.A. | Processes for the preparation of nitrosamine-free N, N-disubstituted nitroaromatic amines and for the stabilization of these compounds against the formation of nitrosamines |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU608808B2 (en) * | 1987-03-02 | 1991-04-18 | Ici Australia Operations Proprietary Limited | Process for removing impurity |
Also Published As
| Publication number | Publication date |
|---|---|
| AU8311087A (en) | 1989-07-06 |
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| MK14 | Patent ceased section 143(a) (annual fees not paid) or expired |