DE107505C - - Google Patents
Info
- Publication number
- DE107505C DE107505C DENDAT107505D DE107505DA DE107505C DE 107505 C DE107505 C DE 107505C DE NDAT107505 D DENDAT107505 D DE NDAT107505D DE 107505D A DE107505D A DE 107505DA DE 107505 C DE107505 C DE 107505C
- Authority
- DE
- Germany
- Prior art keywords
- nitrotoluene
- solid
- chloro
- chlorine
- product
- 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.)
- Expired
Links
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 229910052801 chlorine Inorganic materials 0.000 claims description 11
- 239000000460 chlorine Substances 0.000 claims description 11
- ZAMOUSCENKQFHK-UHFFFAOYSA-N chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 11
- 238000002844 melting Methods 0.000 claims description 9
- 239000007795 chemical reaction product Substances 0.000 claims description 4
- 239000000969 carrier Substances 0.000 claims description 3
- 239000012263 liquid product Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims 1
- 239000007787 solid Substances 0.000 description 13
- 239000000047 product Substances 0.000 description 11
- BSQRMWZONNXDAD-UHFFFAOYSA-N 5-chloro-6-methyl-5-nitrocyclohexa-1,3-diene Chemical compound CC1C=CC=CC1(Cl)[N+]([O-])=O BSQRMWZONNXDAD-UHFFFAOYSA-N 0.000 description 8
- 238000005660 chlorination reaction Methods 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- PLAZTCDQAHEYBI-UHFFFAOYSA-N 2-Nitrotoluene Chemical compound CC1=CC=CC=C1[N+]([O-])=O PLAZTCDQAHEYBI-UHFFFAOYSA-N 0.000 description 5
- 239000003921 oil Substances 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- 235000011121 sodium hydroxide Nutrition 0.000 description 3
- ZXVONLUNISGICL-UHFFFAOYSA-N 4,6-dinitro-o-cresol Chemical group CC1=CC([N+]([O-])=O)=CC([N+]([O-])=O)=C1O ZXVONLUNISGICL-UHFFFAOYSA-N 0.000 description 2
- KUGFODPTKMDJNG-UHFFFAOYSA-I Antimony pentachloride Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[SbH3+3] KUGFODPTKMDJNG-UHFFFAOYSA-I 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N HCl Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- -1 acetyl compound Chemical class 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- VLZLOWPYUQHHCG-UHFFFAOYSA-N nitromethylbenzene Chemical compound [O-][N+](=O)CC1=CC=CC=C1 VLZLOWPYUQHHCG-UHFFFAOYSA-N 0.000 description 2
- 239000012265 solid product Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- VDEXMYMRDWWWAE-UHFFFAOYSA-N 1-chloro-2-(nitromethyl)benzene Chemical compound [O-][N+](=O)CC1=CC=CC=C1Cl VDEXMYMRDWWWAE-UHFFFAOYSA-N 0.000 description 1
- RZIICHLRUUEKIO-UHFFFAOYSA-N 2-[bromo(chloro)amino]benzoic acid Chemical compound OC(=O)C1=CC=CC=C1N(Cl)Br RZIICHLRUUEKIO-UHFFFAOYSA-N 0.000 description 1
- INRGAIXSCJBTQW-UHFFFAOYSA-N 6-chloro-6-methylcyclohexa-2,4-dien-1-amine Chemical group CC1(Cl)C=CC=CC1N INRGAIXSCJBTQW-UHFFFAOYSA-N 0.000 description 1
- YOERAJJGEYUYJW-UHFFFAOYSA-N 6-chloro-6-nitrocyclohexa-2,4-diene-1-carbaldehyde Chemical compound [O-][N+](=O)C1(Cl)C=CC=CC1C=O YOERAJJGEYUYJW-UHFFFAOYSA-N 0.000 description 1
- AGEZXYOZHKGVCM-UHFFFAOYSA-N Benzyl bromide Chemical compound BrCC1=CC=CC=C1 AGEZXYOZHKGVCM-UHFFFAOYSA-N 0.000 description 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N Benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L Iron(II) chloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- BPEXTIMJLDWDTL-UHFFFAOYSA-N N-(2-methylphenyl)acetamide Chemical compound CC(=O)NC1=CC=CC=C1C BPEXTIMJLDWDTL-UHFFFAOYSA-N 0.000 description 1
- QFCSRGLEMDRBMN-UHFFFAOYSA-N N-(2-methylphenyl)nitramide Chemical compound CC1=CC=CC=C1N[N+]([O-])=O QFCSRGLEMDRBMN-UHFFFAOYSA-N 0.000 description 1
- SHLTXWFNRJQZTQ-UHFFFAOYSA-N N-chloro-2-methylaniline Chemical class CC1=CC=CC=C1NCl SHLTXWFNRJQZTQ-UHFFFAOYSA-N 0.000 description 1
- PFDHBJNLFOINAY-UHFFFAOYSA-N [chloro(dinitro)methyl]benzene Chemical compound [O-][N+](=O)C(Cl)([N+]([O-])=O)C1=CC=CC=C1 PFDHBJNLFOINAY-UHFFFAOYSA-N 0.000 description 1
- BVJSGOYEEDZAGW-UHFFFAOYSA-N [chloro(nitro)methyl]benzene Chemical compound [O-][N+](=O)C(Cl)C1=CC=CC=C1 BVJSGOYEEDZAGW-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating Effects 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 230000000875 corresponding Effects 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 239000011344 liquid material Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000006396 nitration reaction Methods 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000001105 regulatory Effects 0.000 description 1
- 230000000717 retained Effects 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
KAISERLICHESIMPERIAL
PATENTAMT.PATENT OFFICE.
Das o-Chlor-o-nitrotoluol wurde bisher nicht aus o-Nitrotoluol erhalten, vielmehr ging man zu seiner Darstellung vom Nitro-o-toluidin aus. Nach den bekannten Thatsachen über die Einwirkung von Chlor auf disubstituirte Benzolderivate konnte nicht angenommen werden, dafs durch directe Chlorirung von o-Nitrotoluol das o-Chlor-o-nitrotoluol entstehen würde, vielmehr war der Eintritt des Chlors in ρ-Stellung zur Methylgruppe anzunehmen. Es hat sich nunmehr gezeigt, dafs unter bestimmten Bedingungen, entgegen der nach der Theorie berechtigten Annahme, die Einwirkung von Chlor auf Nitrotolüol zu dem o-Chlor-onitrotoluol führt. Zur Darstellung von o-Chloro-nitrotoluol läfst man die der Theorie entsprechende Menge Chlor auf möglichst reines (d. h. möglichst frei von ρ-Nitrotolüol und Nitrothiotholen) o-Nitrotoluol in Gegenwart von Chlorüberträ'gern, wie Jod, Eisenchlorid, Antimonpentachlorid etc., einwirken. Die Temperatur erhöht sich immer von selbst allmä'lig bis gegen ioo°. Während das Verfahren schon bei Anwendung von 2 bis 3 pCt. Chlorüberträ'gern ohne Regelung der Temperatur ungefähr 1J3 der theoretischen Ausbeute an festem o-Chlor-o-nitrotoluol liefert, erhält man bessere Ergebnisse, wenn man viel Chlorüberträger anwendet und gleichzeitig die Reactionstemperatur möglichst niedrig auf ca. 20 bis 500 hält.The o-chloro-o-nitrotoluene has not yet been obtained from o-nitrotoluene; rather, nitro-o-toluidine was used as the starting point for its preparation. According to the known facts about the action of chlorine on disubstituted benzene derivatives, it could not be assumed that o-chloro-o-nitrotoluene would result from direct chlorination of o-nitrotoluene; rather, the entry of chlorine in ρ-position to the methyl group was to be assumed. It has now been shown that under certain conditions, contrary to the theoretical assumption, the action of chlorine on nitrotoluene leads to o-chloro-oneitrotoluene. To prepare o-chloronitrotoluene, the amount of chlorine corresponding to the theory is allowed to act on the most pure (ie as free as possible from ρ-nitrotoluene and nitrothiothols) o-nitrotoluene in the presence of chlorine carriers such as iodine, iron chloride, antimony pentachloride, etc. . The temperature increases gradually by itself to about 100 °. While the procedure already applies when using 2 to 3 pCt. Chlorüberträ'gern without regulation of the temperature provides about 1 J 3 of the theoretical yield of solid o-chloro-o-nitrotoluene, better results are obtained when one uses much chlorine carrier and at the same time keeps the Reactionstemperatur as low as possible to about 20 to 50 0th
500 g ganz trockenes, möglichst reines o-Nitrotoluol werden mit ca. 100 g Antimonpentachlorid versetzt und nun so lange trockenes Chlor eingeleitet, bis die Gewichtszunahme des Reactionsproductes ca. 130 g beträgt. Das Reactionsgefäfs wird von aufsen mit fliefsendem Wasser oder dergl. gekühlt und der Chlorstrom derartig geregelt, dafs die Temperatur des Reactionsgemisches ca. 30 bis 400 beträgt. Es ist wichtig, dafs eine Ueberchlorirung vermieden wird. Das Reactionsproduct wird mit verdünnter Salzsäure, Wasser und Natronlauge gewaschen und mit überhitztem Wasserdampf übergetrieben. Das übergehende gelblich gefärbte OeI läfst sich durch Stehenlassen und Absaugen bei niedriger Temperatur (ca. -f- 20) in ein festes und ein flüssiges Product trennen. Das feste Product, etwa 30 bis 40 pCt. des Ganzen betragend, hat den Schmelzpunkt 370, Siedepunkt ca. 236 bis 2380, und erweist sich durch die bei der Oxydation mit alkalischem Permanganat entstehende ο - Chlor - ο - nitrobenzoesäure vom Schmelzpunkt 163 ° (aus Wasser) bezw. 161° (aus Benzol) als o-Chloro-nitrotoluol. Approx. 100 g of antimony pentachloride are added to 500 g of completely dry, as pure as possible, o-nitrotoluene, and dry chlorine is then passed in until the increase in weight of the reaction product is approximately 130 g. The Reactionsgefäfs from without is cooled with water or the like fliefsendem., And the chlorine stream regulated in such a way the temperature of the Reactionsgemisches DAF about 30 to 40 is 0. It is important to avoid over-chlorination. The reaction product is washed with dilute hydrochloric acid, water and sodium hydroxide solution and blown over with superheated steam. The passing over yellowish oil läfst on standing and suction at low temperature (about 0 -f 2) separate into a solid and a liquid product. The solid product, about 30 to 40 pct. of the whole, has a melting point of 37 0 , boiling point approx. 236 to 238 0 , and is shown by the ο - chlorine - ο - nitrobenzoic acid with a melting point of 163 ° (from water) or. 161 ° (from benzene) as o-chloro-nitrotoluene.
Zur Darstellung des o-Chlor-o-nitrotoluols ist es nothwendig, von möglichst reinem o-Nitrotoluol auszugehen, indem aus sogen, flüssigen Nitrotolüol der feste Körper kaum erreichbar ist. Das o-Chlor-o-nitrotoluol hat nämlich die Eigenschaft, sich vermöge seines niedrigen Schmelzpunktes schon durch geringe Verunreinigungen zu verflüssigen und dann für weitere Operationen unbrauchbar zu werden. So erklärt sich auch, dafs bei der Chlorirung des ο-Nitrotoluols ca. zwei Drittel des Reactionsproductes flüssig bleiben, im Wesentlichen aber dennoch dasselbe sind wie das feste Product, indem geringe Mengen von Nebenproducten die Verflüssigung bewirken.For the representation of the o-chloro-o-nitrotoluene it is necessary to start from o-nitrotoluene which is as pure as possible, by liquid Nitrotolüol the solid body hardly is attainable. The o-chloro-o-nitrotoluene has the property of being by virtue of its low melting point to be liquefied by minor impurities and then to become unusable for further operations. Thus it is also explained that in the case of chlorination of the ο-nitrotoluene about two thirds of the reaction product remain liquid, essentially but are nevertheless the same as the solid product, in that small quantities of By-products cause liquefaction.
Das Vorhandensein des Nebenproductes bedingt ein verschiedenes Verhalten des festen und flüssigen Chlorirungsproductes gegen Brom, indem aus dem festen o-Chlor-o-nitrotoluol leicht das Benzylbromid gebildet wird, während aus dem flüssigen Chlorirungsproduct nur eine Chlorbromanthranilsöure erhalten werden kann. Trotzdem sind das feste und flüssige Chlorirungsproduct im Wesentlichen identisch. Am einfachsten ergiebt sich dies daraus, dafs aus beiden Producten das gleiche Dinitroproduct zu erhalten ist. Zu seiner Gewinnung löst man die Substanzen in dem gleichen Gewichte starker Salpetersäure von specifischem Gewicht .1,52 und giebt die doppelte Menge gewöhnlicher Schwefelsäure hinzu, indem durch Wasserkühlung dafür gesorgt wird, dafs die Temperatur nicht über 500 steigt. Nach mehrmaligem Umkrystallisiren ergiebt sich der Schmelzpunkt des aus festem Ausgangsmaterial erhaltenen bisher unbekannten Dinitro- (2 : 3) -chlortoluols zu 106 bis 1070. Das Dinitroproduct des flüssigen Materials ergiebt abgesogen über die Hälfte festen Materials, das nach häufigem Umkrystallisiren sich auch als Dinitro- (2 : 3) -chlortoluol vom Schmelzpunkt 106 bis 1070 erweist. Aus dem öligen Theil des Nitroproducts läfst sich durch wiederholtes Behandeln mit starker Natronlauge schliefslich auf dem Wasserbade noch ein sehr erheblicher Antheil des gleichen Dinitrochlortoluols erhalten. Durch die Behandlung mit Natronlauge wird höchstwahrscheinlich das bei der Chlorirung von Nitrotoluol und Nitrirung gebildete Dichlordinitroproduct gelöst, weil es saurer ist als das Monochlordinitroproduct. Somit dürfte das feste und das flüssige Chlorproduct bis auf geringe Mengen verunreinigender OeIe identisch sein.The presence of the by-product causes a different behavior of the solid and liquid chlorination product towards bromine, in that benzyl bromide is easily formed from the solid o-chloro-o-nitrotoluene, while only a chlorobromanthranilic acid can be obtained from the liquid chlorination product. Nevertheless the solid and liquid chlorination products are essentially identical. The simplest way of doing this is when the same dinitro product can be obtained from both products. For its recovery, the substances are dissolved in an equal weight concentrated nitric acid of specific gravity .1,52 and gives twice the amount usually sulfuric acid are added, by providing water cooling for the temperature not exceeding 50 DAF 0 increases. After repeated recrystallization, the melting point of the hitherto unknown dinitro (2: 3) chlorotoluene obtained from the solid starting material is 10 6 to 10 7 0 . The Dinitroproduct it follows the liquid material drawn off over half of the solid material, which gradually after repeated recrystallization as dinitro- (2: 3) proves -chlortoluol of melting point 106-107 0th A very considerable proportion of the same dinitrochlorotoluene can finally be obtained from the oily part of the nitro product by repeated treatment with strong sodium hydroxide solution on the water bath. By treatment with caustic soda, the dichlorodinitro product formed in the chlorination of nitrotoluene and nitration is most probably dissolved, because it is more acidic than the monochloroditro product. Thus the solid and the liquid chlorine product should be identical except for small amounts of contaminating oils.
Auch die Chlortoluidine, welche durch Reduction des Chlornitrotoluols (fest und flüssig) auf den gewöhnlichen Wegen erhalten werden, sind identisch. Es sind OeIe, die selbst durch Kältemischungen nicht fest zu erhalten sind. . Es liegt also o-Chlor-o-toluidin (Berichte 20, Seite 2417 und .2418) vor. Der Schmelzpunkt des Acetyltoluidins liegt allerdings bei dem festen Ausgangsproduct nicht bei 1360 (wie 1. c. angegeben), sondern bei 157 bis 159. Denselben Schmelzpunkt zeigt das Acetyltoluidin aus flüssigem Product nach wiederholtem Umkrystallisiren aus Alkohol und Wasser.The chlorotoluidines, which are obtained by reducing chloronitrotoluene (solid and liquid) in the usual ways, are also identical. They are oils that cannot be retained in a solid state even with cold mixtures. . So there is o-chloro-o-toluidine (Reports 20, page 2417 and .2418). However, the melting point of the solid starting Acetyltoluidins is not Product at 136 0 (as in 1 c. Specified), but at 157 to 159. The same melting point shows the Acetyltoluidin of liquid product after repeated recrystallization from alcohol and water.
Auch die Tolidine aus flüssigem und festem Chlorirungsproduct sind identisch (Schmelzpunkt 20i°, Acetylverbindung oberhalb 250°).The tolidines from liquid and solid chlorination products are also identical (melting point 20 °, acetyl compound above 250 °).
Das feste o-Chlor-o-nitrotoluol soll infolge seiner Ueberführbarkeit in o-Chlor-o-nitrobenzylbromid als Ausgangsmaterial für o-Chloro-nitrobenzaldehyd und o-Chlorindigo dienen.The solid o-chloro-o-nitrotoluene should as a result its convertibility into o-chloro-o-nitrobenzyl bromide as a starting material for o-chloro-nitrobenzaldehyde and o-chloroindigo serve.
Claims (1)
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE107505C true DE107505C (en) | 1900-01-01 |
Family
ID=377572
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DENDAT107505D Expired DE107505C (en) |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE107505C (en) |
-
0
- DE DENDAT107505D patent/DE107505C/de not_active Expired
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