DE2016691A1 - Process for the preparation of 6-chloropyridazinium compounds - Google Patents

Description

Our reference: O. Z, 26 722 WB / Be 6700 Ludwigshafen, 6.4.1970

Process for the preparation of 6-chloropyridazinium compounds

The invention relates to a method for producing 6-ChlOrpyridaziniumverbindungen by reaction of pyridazone- (6) with phosgene, thiophosgene or oxalyl chloride.

It has been found that 6-chloropyridazinium compounds of general formula

I,

where R ₁ , R ₂ and R, can be identical or different and each represent an aliphatic, cycloaliphatic, araliphatic or aromatic radical and X stands for a chlorine atom, in addition R ₁ and R ₂ each also represent a hydrogen atom, a halogen atom, an alkoxy group , an alkyl mercapto group, a mercapto group, a nitro group, an aromatic radical bonded via an azo group and R »can also mean a heterocyclic radical, is advantageously obtained when pyridazone- (6) of the general formula

II,

in which R ₁ , R 1 and R, which have the abovementioned meaning, are reacted with phosgene, thiophosgene or oxalyl chloride in the presence of an organic solvent which is inert under the reaction conditions.
581/69 - 2 -

1098 A3 / 1932

- 2 - O. Z. 26 722

The implementation can, in the case of the use of 1-Phenylpyridazon- (6) and phosgene are represented by the following formulas:

+ COCl

2 ^ «r & Λ θ

Gl + CO,

The process according to the invention provides a large number of 6-chloropyridazinium compounds in a simple manner Yield and purity.

Preferred starting materials II and correspondingly preferred end products I are those in whose formulas R .., Rp ^UIU * ^ 3 can be the same or different and in each case an alkyl radical with 1 to 7 carbon atoms, a cyelopentyl or cyclohexyl radical, an aralkyl radical with 7 to 12 Mean carbon atoms or a phenyl radical, and X stands for a chlorine atom, in addition R ^ and Rp also each represent a hydrogen atom, a chlorine atom, a bromine atom, an alkoxy group, an alkylmereapto group each with 1 to 4 carbon atoms, a mercapto group, a nitro group, one above can denote an azo group bonded phenyl radical and R- can also denote a 5- or 6-membered, heterocyclic radical which can contain a nitrogen atom and / or an oxygen atom or a further nitrogen atom. The radicals mentioned can also be substituted by groups and / or atoms which are inert under the reaction conditions, for example chlorine atoms, bromine atoms, fluorine atoms, alkyl, alkoxy groups each having 1 to 4 carbon atoms.

There are, for example, possible starting materials II: 1-phenyl-, 1-n-butyl-, 1-p-chlorophenyl-, 1-o-nitrophenyl-, 1-m-nitrophenyl-, 1-m-nitro-, 1 -p-chlorophenyl-, 1-isobutyl-, 1-o, p-bichlorophenyl-, 1-cyclohexyl-, 1-benzyl-, 1-BrOm- (Z ¹ ^ cyclohexyl-, 1-methyl-, 1-m- Trifluoromethyl-, 1-p-ethoxyphenyl-, 1-pyridylpyridazon- (6); 3- or 4-chloro-, ethyl-, cyclohexyl-, phenyl-, benssoyl-, methoxy-, mercapto- , Propylmercapto-, phenylazo-, nitro-pyridazone- (6).

109843/1932 " ³ "

- 3 - O, Z. 26 722

Starting material II was known with the stoichiometric amount or with an excess of acid halide, preferably with a 0.1 to 3-fold excess over the stoichiometric Amount, implement.

The reaction is carried out generally -in a temperature between 0 and 100 ⁰ C, preferably between 20 and 80 ⁰ C, under atmospheric or superatmospheric pressure, continuously or discontinuously. An organic solvent which is inert under the reaction conditions is used in the reaction, suitably anhydrous. Examples of organic solvents that can be considered are: carboxamides disubstituted on the nitrogen, such as dimethylformamide, dimethylacetamide; Chlorinated hydrocarbons such as chloroform, methylene chloride, perchlorethylene; aromatic hydrocarbons such as. Benzene, nitrobenzene, toluene, xylene, diisopropylbenzene, tetralin; Ethers such as diethyl, diisobutylating, tetrahydrofuran, dioxane; Carboxylic acid esters such as ethyl acetate, butyl propionate. The organic solvent is generally used in an amount of 100 to 5,000 percent by weight, based on starting material IX.

The implementation can be carried out as follows: A solution of the 'starting material II in an anhydrous, organic Solvent is for 5 minutes to 4 hours at the Maintained reaction temperature, slowly reducing the acid halide is initiated '* The end product falls from the reaction mixture in the crack gel -crystalline and is in the usual way through

separated w .Ii -general is under moisture- ^ worked. The end product is usually so pure, that an Umkiristallisierung is not and can not be necessary can be implemented directly.

Di ^ madfi "iömr * method; the invention can produce new ^w erbln ^ ün ^ e %% ijid · valuable starting materials. For the production of voir '" P ^ M ^ iftΪan. So can ouch; to them by conversion with subs1ri ^; door1rte1i arylemihiBn dyes are obtained which are in. an amount of 0.3 ^? up to 6 percent by weight, based on the, ...., weight iB ^ hge iPäs'ermaterial, · ^ polyamide fibers in organic solvents. bel ^r GCf to -80 ° C-dyeing, Tpid-water-resistant, .pa, stell-

1 0 9843/1 9 3 2 ^J "

- 4 - O.Z. 26 722

colored shades result. The aforementioned organic solvents can serve as a coloring medium.

The parts given in the examples are parts by weight. They relate to parts by volume like the kilogram to the liter.

example 1

In a solution of 17.4 parts of 1-phenylpyridazone in 200 parts of anhydrous benzene are at
initiated during 2 hours.

anhydrous benzene are slowly added at 5O ⁰ C. 15 parts of phosgene

The resulting pyridazinium salt is filtered off with suction while removing moisture. Is obtained 21 parts (95 i> of theory) of i-phenyl-e-chloro-pyridaziniumchlorid of melting point 209 to 211 ⁰ C (dec.)

Example 2

In a solution of 17.4 parts of 1-phenylpyridazone in 200 parts of anhydrous Chlorofori
2 hours initiated.

anhydrous chloroform, 13 parts of phosgene ^{are at 5O 0 C during}

The resulting pyridazinium salt is suctioned off with the exclusion of moisture. Is obtained 20 parts (90 £ of theory) of i-Phtnyl-6-chloro-pyridaEiniumchlorid the FPS 209 211 ⁰ bit C

Example 3

2UR LS Hung of 2 T "il" n 1 - ( "- trifluoro» ethyl) -pyridaeon in 50 Teiltn toluene are added 1.5 Voluaenteile Oialylchlorid and heated for 2 hours at 45 ⁰ C.

The resulting pyridazinium salt is suctioned off with exclusion of moisture. This gives 2.3 parts (94 ^ of theory) in-trifluoromethyl-e-chloro-pyridaziniumchlorid mp: 172 to 174 ⁰ C (dec.).

- 5 10 9 8 ^ ^{3/1932 0RJGlNAL 1NSP £ GTE} °

- · 5 ■■ '- ■ Ö.Z.26 722

Example 4

To solution of 10! Rush 1-methyl-pyridazone in 200 parts of anhydrous tetrahydrofuran werden20 Yolümenteile Oxälylchlorid and heated 1.5 hours to 45 ⁰ C.

The precipitating end product is suctioned off with exclusion of volatility. Is obtained 14 parts (95 $ of theory) of 1-methyl-6-chloro-pyridaziniumchlorid from FPJ 163-165 ⁰ C (dec.) ·

Example 5.

1.5 parts by volume of oxychloride are added to the solution of 2 parts of 1-phenyl-3-chloropyridazone in 50 parts of anhydrous perchlorethylene, and the solution is ^{heated to 50 0} O for 2 hours. The precipitating end product is suctioned off with the exclusion of moisture. 2 parts (80-6 of theory) of i-phenyl-1-4 -dichloropyridazine chloride with a melting point of 233 to 234 ⁰ G (decomp.) Are obtained. .

"- ■." ■ -. ■ Example 6 ■.;. ■; ' '"

2 parts of thiophosgene ^{are added at 40 °} C. for 2 hours to the solution of 2 parts of i-phenyl-4-chloropyridazone in 30 parts of anhydrous benzene. The pyridazinium chloride crystallizes out and is filtered off with suction with the exclusion of moisture. This gives t, 9 parts (75 $ of theory) of 1-phenyl ^ 6-dichlorpyridaziniumchlorid mp: 209 to 211 ⁰ C (dec,).

into the solution; from % Teilin ^ -ÖyciöhiiEyipyriiäzön itfc 1ÖÖ anhydrous ethyl acetate werxWi slowly 2 Tiili Έϊ & ύ & η appliedltttp ϊΙΝΙά ^{for 2 hours at -50 e O.} iÄtstaaiiäel

i we! iiiesäugtv Maii ifhilf ~% jo Teili (90 \ - $ dii lö & e ^ i-ö-onlo Ip * \ $ £

-.'.- - ■■ - e a

- 6 - O.Z. 26 722

Example 8

2 parts of i-phenyl-3-phenyl-azo-pyridazone are dissolved in 50 parts of benzene and heated with 2 Yolumenteilen oxalyl chloride for 2 hours at 5O ⁰ C. The resulting pyridazine chloride is filtered off with suction. To give 2 parts (85 # of theory) of 1-phenyl-5-pheny1-azo-6-chloro-pyridazinchlorid from Pp: 150 to 155 ⁰ C (dec.).

Example 9

1 part of i-phenyl-3-phenyl-pyridazon is anhydrous in 50 parts Dissolved chloroform and added 1 part by volume of oxalyl chloride

Heated for 2 hours at 5O ⁰ C. The pyridazinium chloride obtained is filtered off with suction with exclusion of moisture. Obtained 1 part (85 1 'of theory) of i-phenyl ^ -phenyl-e-chloro-pyridaziniumchlorid from Pp: 242-247 ⁰ C.

Example 10

For Iiöflung of 2 parts of 1- (m-trifluoromethyl) phenyl-4-chlorpyridazon in 50 parts of dioxane are 2 Yolumenteile oxalyl chloride was added at 60 ⁰ C. After 5 minutes, the crystalline end product precipitates and is filtered off with suction after cooling. Maii obtained 2.3 parts (95 * of theory) of 1- (m-Trifloor-methyl) -plienyl ~ 4,6-diohlor-pyridaiiniumchlorid of Tp: 221 bie 223 ⁰ G (Zere.).

- 7 -1098 A3 / t932

Claims (2)

.- .; ■ '■ - 7 - 0.2. 26 722 Claims ό '■ - ^ - ■■ - ■ · ^; ■■ - ■■ - ty Process for the production of 6-chloropyridaeinium compounds the general formula θ
II, where R ₁ , R «and R * can be the same or different and each mean an aliphatic, cycloaliphatic, araliphatic or aromatic radical and I stands for a chlorine atom, in addition Rj and R ₂ each also have a hydrogen atom, a halogen atom, a Alkoxy group, an alkyl mercapto group, a mercapto group, a nitro group, an aromatic radical bonded via an azo group and R can also mean a heterocyclic radical, characterized in that one pyridazone- (6) of the general formula II in which R ₁ , R ₂ and R _{3 have} the aforementioned meaning, if phosgene, thiophosgene or oxalyl chloride are converted in the presence of an organic solvent which is inert under the reaction conditions. - 8 1 0 9 8 A 3/1 9 3 2 - 8 - O. Z. 26 722 2) 6-chloropyridazinium compounds of the general formula where R ^, I ^ and R, can be identical or different and each represent an aliphatic, cycloaliphatic, araliphatic or aromatic radical and X stands for a chlorine atom, in addition R ₁ and R ₂ each also represent a hydrogen atom, a halogen atom, an alkoxy group , an alkyl mercapto group, a mercapto group, a nitro group can denote an aromatic radical bonded via an azo group and R- * can also denote a heterocyclic radical. Badische Anilin- & Soda-? Abrik AG 1098 A3 / 1-932