DE2647596A1 - DIISOTHIAZOLS AND THE PROCESS FOR THEIR MANUFACTURING - Google Patents

Description

VON KREISLER SCHONWALD MEYER EISHOLD FUES VONKREISLER KELLER

PATENT LAWYERS Dr.-Ing. by Kreisler + 1973

Dr.-Ing. K. Schönwald, Cologne Dr.-Ing. Th. Meyer, Cologne Dr.-Ing. K. W. Eishold, Bad Soden Dr. J. F. Fues, Cologne Dipl.-Chem. Alek von Kreisler, Cologne Dipl.-Chem. Carola Keller, Cologne Dipl.-Ing. G. Selling, Cologne

AvK / Ax

5 COLOGNE 1 2o.1o.1976

DEICHMANNHAUS AT THE MAIN RAILWAY STATION

E.I, du Pont de Nemours and Company, Wilmington, Delaware 19898 (U.S.A.).

Diisothiazoles and process for their preparation

The invention relates to diisothiazoles, in particular the tricyclic heterocyclic ring system 1,4-dithiine / 2,3-c; 6jS-c ^ Vdiisothiazole and its ring-substituted Derivatives.

Publications Discussing the Isothiazole Tricyclic Ring System describe according to the invention are not known to the applicant. U.S. Patent 3,110,344 describes the bicyclic p-dithiine / c_ ~ isothiazole-3,5,6-tricarbonitrile the formula

NC I CH

as a by-product of the production of tetracyane-1,4-dithiine. In J.Am.Soc. 84 (1962) 4746 is the production this tricarbonitrile by reacting tetracyane-1,4-dithiine with sulfur, iodine and sodium iodide at 25 ° C.

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Telephone: (0221) 234541-4 Telex: 888 2307 dopa d Telegram: Dompatent Cologne

The diisothiazoles according to the invention have the structure __

wherein the two radicals R are the same and stand for -H, -CN, -COCl, -CO ₂ R ¹ , -CONR ² R ³ or -CO ₂ "(alkyl),
R for -H, alkyl with 1 to 5 carbon atoms, phenyl or

Benzyl stands and

R ² and R ^{3 represent} -H, alkyl having 1 to 5 carbon atoms, phenyl or a phenyl radical substituted by alkyl radicals, alkoxy radicals, nitro groups, halogen atoms or dialkylamino groups, the alkyl radical containing 1 to 5 carbon atoms.

The invention further comprises the preparation of the above-mentioned compound by a process the essential stage of which is that one tetracyane-1,4-dithiin the formula

NC

NC

or

4,5-Dicyan-1,3-dithiolen-2-one of the formula

NC

with sulfur in 1,2-dimethoxyethane (glyme) as a solvent at a temperature in the range of 50 to

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280 ° C, preferably 75 to 85 ° C, in the presence of a basic catalyst. The cyano groups can optionally converted into acid groups, amide groups or ester groups by customary processes.

The 3,7-dicyan-1,4-dithiin / 2,3-c; 6,5-c_Vdiisothiazole of the formula (I), in which R stands for CN, is prepared by reacting tetracyano-1,4-dithiine or 4,5-dicyano-1,3-dithiolen-2-one with sulfur in the presence of a catalyst in 1,2-dimethoxyethane as a solvent according to the following reaction scheme:

CN

more basic
8 catalyst

The reactants can be mixed in any order, but mixing is preferred the catalyst and the sulfur with the solvent before, heated briefly to the reflux temperature to the To dissolve reactants, and finally gives the tetracyano-l, 4-dithiine or 4,5-dicyano-l, 3-dithiolen-2-one to.

Tetracyan-1,4-dithiine is produced in the manner described in the aforementioned US Pat. No. 3,110,344 and 4,5-dicyanl, 3-dithiolen-2-one prepared in the manner described in US Pat. No. 3,140,295.

The reaction temperature is not particularly critical as long as the reaction temperature is at least

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"t"

about 50 ° C is worked. If at significantly below reaction temperatures lying around 50 ° C, e.g. at: room temperature, the reaction proceeds not with formation of the desired 3,7-dicyano-1,4-dithiino / 2,3-c; 6,5-c_Vdiisothiazole. Higher reaction temperatures, for example up to about 280 ° C., can be applied. It is preferred to work at temperatures of about 75 to 85 ° C., since the reaction is expedient carried out near the reflux temperature of the solvent (83-84 ° C) approximately at normal pressure will.

The quantitative ratio of the reactants, i.e. sulfur to tetracyano-1,4-dithiine or 4,5-dicyano-1,3-dithiolen-2-one, is not critically important. However, since an equivalent ratio of at least 2: 1 for sulfur: tetracyano-1,4-dithiine or 4,5-dicyanl, 3-dithiolen-2-one for the complete implementation of the dithiin or dithiols is required, a Equivalent ratio of these reactants of at least 2: 1 is preferred. It is also preferred with a higher equivalent ratio up to about 5: 1 worked, since the reaction in the presence of excess Sulfur runs faster. If excess sulfur is used and / or the reaction time during the reaction with dithiine is shortened, a by-product together with dicyan-1,4-dithiine // !, 3-c; 6,5-cJVdiisothiazole formed. Since the by-product in the Reaction medium is more soluble, it can be easily separated from the main product.

Suitable basic catalysts for the reaction are, for example, tertiary aliphatic amines, polysulfides, Alkali iodides and alkali sulfides. Special catalysts within this group are sodium iodide, Potassium iodide, lithium iodide, sodium polysulfide, potassium polysulfide, Triethylamine, tri-n-propylamine, diiso-

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propylethylamine, diisopropylmethylamine, tri-n-butylamine, NyN-dimethylcyclohexylamine, alkali and tetraalkylammonium salts of bis (2-mercapto-l, 2-dicyanovinyDsulfid, e.g. the sodium, potassium, tetramethyl- ammonium, tetraethylammonium, tetrapropylammonium and tetra-n-butyammonium salts. Preferred as catalysts become alkali iodides, especially sodium iodide, because of the high product yields obtained and tertiary aliphatic amines because of their high catalytic effectiveness in terms of shortening the Response times. The molar ratio of catalyst to Tetracyano-1,4-dithiine or 4,5-dicyano-1,3-dithiolen-2-one is preferably in the range from 1:20 to 1: 5.

The response time is not critically important. It is advisable to use times of about 1 to 24 hours worked depending on the selected catalyst. Examples 1 through 5 and 21 illustrate this Preparation of compound I (R = CN).

The compounds according to the invention in which R = -H,

12 3 '-COCl, -CO ₂ R and -CONR R, can easily be omitted

3,7-dicyano-1,4-dithiino / 2,3-c; 6,5-cjy ^diisotniazo1 (R = CN in formula I) according to known methods for converting

Conversion of nitrile groups into amides, carboxylic acids, ' Manufacture esters and acid chlorides. For example, the above-mentioned compound causes the reaction hydrolytic decarboxylation with sulfuric acid at elevated temperatures, a product of the Formula I wherein R is hydrogen is obtained as illustrated in Examples 6 and 7.

As an alternative, basic hydrolysis of the above compound with aqueous potassium hydroxide and then acidifying the corresponding dicarboxylic acid (formula I, where R = -COpH) » as illustrated in Example 8. By hydrolysis with

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concentrated hydrochloric acid (Example 9) is also used the dicarboxylic acid obtained.

The dicarboxylic acid chloride (formula I, in which R = -COC1) becomes obtained from the dicarboxylic acid by reaction with conventional reagents, e.g. thionyl chloride or PCI- (Example 10). The dicarboxylic acid chloride can in turn be used for the preparation of amides by reaction with a suitable amine (Examples 11 and 15 to 20) or for the preparation of esters by reaction with an alcohol (Examples 12-14) can be used.

The esters (formula I, where R = -COpR) can also be prepared directly from the dicarboxylic acid by reaction with an alcohol in the presence of an acidic catalyst I. Furthermore, salts (formula I, in which R = -C0p ~ (alkyl) ₄ N +) can be prepared from the dicarboxylic acid by reaction with a tetraalkylammonium hydroxide (Example 22).

The following examples describe embodiments of the invention. In these examples all relate Quantities in parts and percentages by weight, unless otherwise stated. The one with a Primed values of the elemental analysis are average values of two or more determinations.

example 1
3,7-dicyano-1,4-dithiine / 2,3-c; 6,5-c.Vdiisothiazole

(Formula 1, R = -CN)

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4.32 g (20 milliequivalents) of tetracyano-1,4-dithiin were added with stirring to a solution of 2.69 g (84 milliequivalents) of sulfur and 0.6 g (2 milliequivalents) of the dipotassium salt of bis (2- mercapto-1,2-dicyanovinyl) sulfide in 200 ml of 1,2-dimethoxyethane. The yellow-green solution turned dark quickly in orange "The reaction mixture was heated overnight at reflux (83-84 ⁰ C). The solution was cooled and the solvent removed under reduced pressure. The residue was extracted with water and filtered to give a crude solid product in a yield of 87%. This crude product was sublimed (about 0.1 mm Hg, oil pump) at 235 ° C and

pure recrystallized twice from toluene, with 3,7-dicyanl, 4-dithiyne / 2 ~, 3-c; 6,5-cJ_7diisothiazole obtained in the form of a pale yellow solid with a melting point of 286-289 ° C became.

Elemental analysis; Calculated for CgN ₄ S ₄ : Found:

Confirm the following spectral values and analysis values the structure of formula I:

A) Maxima in the infrared spectrum (KBr): 4.50 s, CN), 6.78 (s), 7.48, 7.58, 7.78 (s), 8.68, 10.43 (s), ll, 85 (s), 12.3O- (s), 14.58, 14.98 Ai.

B) Dipole moment, measured at 25 ° C. in dioxane: u = 3.82 D; 3.59 D.

Further analysis values were determined on another sample of the product:

C) Maxima in the UV spectrum (CH ₃ CN):% max 338 nm (6 1Q900), 278 (14950), 218 (25J0OO).

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£ 3 20th N_ 45 S. 34, 6th 20th , 0 45 , 7 34, , 0 , 4

D) The nuclear magnetic resonance ^{spectrum with carbon-13 (13} C-NMR) was recorded in dimethylsulfoxide -d _fi (DMS0-d _fi ) at 100.degree. Chromium acetylacetonate (0.01 g) was added to fix the signals. Analysis found four non-equivalent carbon atoms at 153.2, 133.0, 127.2 and 108.3 (CN) ppm of tetramethylsilane as a reference.

E) The mass spectral analysis with high resolution gave a measured m / e value of 279.8988, which agreed with the molecular formula CgN ₄ S ₄ (calculated for CgN ₄ S ₄ : m / e 279.9006).

F) The crystal and molecular structures of 3,7-dicyanl, 4-dithiin / 2,3-c; 6,5-cVdiisothiazole were determined from three-dimensional X-ray diffraction values, which were determined by counting methods, e.g. with a picker diffractometer. The molecular conformation is clearly defined as trans, as Formula I shows. The molecular point symmetry is Cp (2) with the twofold axis perpendicular to the 1,4-sulfur atoms The molecule is along the 1,4-S "" S direction and folded planar within 0.04 8 on either side of the fold. The folding angle is 144.9 °, measured by the angle between the two five-membered isothiazole rings. The folded molecules are staggered along the b-axis with 3.808 S between the sulfur atoms on neighboring molecules. The perpendicular distance between the isothiazole rings is 3.614 8.

The crystals are monoclinic, space group C 2 / c, with a_ = 12.836 ^ 0.006, t) = 3.808 ^ 0.002, £ = 21.060 + 0.008 8 and ß = 104.91 + 0.03 °. The density for four molecules per cell is 1.87 g cm " ^3. On the basis of these values it is clearly established that the molecular structure of 3,7-dicyan- 1,4-dithiin / 2,3-c; 6.5 -cVdiisothiazole the trans form

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as shown in Formula I.

The dipotassium salt of bis (2-mercapto-1,2-dicyanovinyl) sulfide used as a catalyst was prepared as follows: 10.8 g (0.05 mol) of tetracyano-1,4-dithiine in 200 ml of acetone was added within 30 minutes added to 16.0 g (0.1 mol) of potassium ethylxanthate in 500 ml of acetone. After stirring for an additional 30 minutes, the solvents were removed under reduced pressure. The residue was extracted several times with 50 ml of low-boiling petroleum ether each time under reflux. The insoluble residue (19 g) was dissolved in 300 ml of acetone and filtered off. 1 liter of chloroform was added to the filtrate. A total of 11 g (65%) of the dipotassium salt of bis (2-mercapto-1,2-dicyanovinyl) sulfide was obtained as a yellow solid with a melting point of 280-285 ° C. (decomposition). The infrared spectrum showed characteristic bands at 4.53 (CSN) and 6.76 u (C = C). The UV spectrum (EtOH) showed X _max 380 nm (6 18,400) and 218 (16,950).

Elemental analysis;

Calculated

Found:

Calculated for CgN ₄ S.

c_ 0 H 17th N 29 , 46 ₃ K ₂ : 29.42 0 , 00 17th , 16 29 , 51 28.70 , 40 , 31 Example 2

3, 7-dicyano-1,4-dithiin / 2,3-c; 6, 5-cJ_7diisothiazole (formula I-, R = -CN) .

An increased yield of dicyan product was obtained as follows: 900 ml of 1,2-dimethoxyethane, 20.25 g (0.633 equivalents) of sulfur and 2.7 g (18 milliequivalents) of sodium iodide were refluxed for 5 minutes. The suspension was cooled to room temperature, whereupon 32.4 g (0.15 equivalents) of tetracyano-1,4-dithiine were added. The reaction mixture was heated reflux for 20 hours (83-84 ⁰ C) and cooled, followed by a few crystals of 3,7-dicyano-l, 4-dithiin / 2 ", 3-c;

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6,5-cVdiisothiazole, the identity of which according to the example 1 had been determined spectral and analytical test methods were added. The mixture was cooled to -78 ° C. for one hour with stirring. The crude product (43.7 g, about 100% yield) was filtered off. By one-time recrystallization from Toluene (using decolorizing charcoal) was the desired compound obtained in pure form.

Examples 3 to 5

Using the catalysts mentioned in the middle column, the yields mentioned in column 3 were on 3,7-dicyan-1,4-dithiine / J, 3-c; 6,5-c_ydiisothiazole obtain.

ί Example catalyst yield, %

3 (C ₂ H ₅ J ₃ N 59

4 K _? P 52

5 diisopropylethylamine (a)

(a) The reaction was carried out for 2.25 hours. A mixture of 3,7-dicyan-1,4-dithiin / 2,3-c; 6,5-cJV-diisothiazole (Yield 40%) with the product II from Example 6 was obtained.

Example 6
1,4-dithiine / 2,3-c; 6,5-c_Vdüsothiazol (Formula 1, R = -H)

A mixture of 0.28 g (1 milliequivalent) 3,7-dicyanl, 4-dithiine / 2,3-c; 6.5-c_Vdiisothiazol, 21 ml of concentrated sulfuric acid and 7 ml of water was used. 15 minutes heated to 170 ° C. The yellow solution was at room temperature

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2ΘΑ7596

chilled temperature and poured onto ice. The suspension was filtered and the solid with 1N sodium hydroxide solution extracted, the desired compound remaining as a colorless solid as residue.

Example 7
1,4-dithiine / 2,3-c; 6,5-c ^ 7diisothiazole

The experiment described in Example 6 was repeated on a larger scale in order to obtain enough product for analysis and characterization. The reaction with sulfuric acid was carried out with 4.6 g of 3,7-dicyanl, 4-dithiin / 2.3-c; Performed cVdiisothiazol 6.5 for 3 hours at 180 ⁰ C. After this time the solution was colorless. The crude product isolated in the manner described in Example 6 was recrystallized from chlorobutane, the desired compound having a melting point of 190 ° to 191 ° C. being obtained in pure form.

Elemental analysis; C_ H N_ j3

Calculated for C ₆ H ₂ N ₃ S ₄ : 31.3 0.88 12.2 55.7 molecular weight 230.34

Found: 32.1 1.42 12.2 54.5

Mass spectral analysis: m / e calculated 229.9101

found 229.9097

NMR (DMSO-dg): (δ) 9.0-9.1 ppm (singlet)

UV: (CH-CN): λ_ 295 nm (£ 11,500), 211 (17,900)

IR (KBr): 3.73 and 3.26 (s, = CH), 6.10 and 6.80 (w), (conjugated, cyclic C = C and / or C = N), 7.59 (s ), 7.75 (s), 11.85 (w), 12.15 (m), 12.35 (w), 12.55 (w),

The use of 1,4-dithiino / 2 ~, 3-c; 6,5-cJ_7diisothiazole fluorescent brightener was illustrated as follows: A sample of multi-ply fabric was immersed in an aqueous suspension of the diisothiazole.

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The suspension was heated to 100 ° C. for 30 minutes. The fabric was taken from the suspension, with distilled Rinsed with water and dried. The dried fabric was exposed to UV light using an untreated Substance examined as a comparative sample. All fabrics in the swatch showed some fluorescence.

Example 8

1,4-dithiine / 2,3-c; 6, S-cVdiisothiazole-S, 7-dicarboxylic acid (Formula 1, R = -C0 "H)

CN

+ KOH

<xx>

1.4 g (25 milliequivalents) potassium hydroxide were dissolved in 25 ml of water. The solution was 1.0 g (3.6 milliequivalents) 3,7-dicyano-1,4-dithiine / 2,3-c; 6,5-cJ_7diisothiazole given. The suspension was bubbled with nitrogen while it slowly increased to reflux temperature was heated. A vigorous stream of nitrogen continued to exist while refluxing passed through to expedite the removal of ammonia. After 4 to 5 hours the solid had settled completely resolved. After cooling to room temperature, the dipotassium salt separated from 1,4-dithiine - / ^ 2,3-c; 6, S-c ^ / diisothiazole-S, 7-dicarboxylic acid from the solution

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away. The salt was filtered off and dissolved in water. The solution was heated to 100 ° C. and treated with 6N hydrochloric acid neutralized. Intense yellow colored crude 1,4-dithiine / 2,3-c; 6,5-cj7dJ.isothiazole-3,7-dicarboxylic acid deposited and isolated from melting point 230-247 ° C. The acid can crystallize Purified from glacial acetic acid and prepared by suspending in hot water and filtering the hot suspension further cleaned. The purified product with a melting point of 230 ° C. (decomp.) Fluoresced on exposure of ultraviolet light.

Elemental analysis; C \ ± jJ S ^

Calculated for CgH ₂ O ₄ N ₂ S ₄ : 30.2 0.63 8.80 40.3 Found: 30.5 1.01 8.72

UV spectrum (separate sample) (EtOH): λ 368 nm (611,700), 277 (4900), 219 (29,500) (0, In-NaOH) λ _a "352 nm (£ 10,900), 273 (3980)

IR (KBr): 3.0-4.0 (broad, Η-bonded -OH), 5.95 (s, carbonyl) 6.66 (s, conjugated C = C and / or C = N), 7.09, 7.50, 8.03 (s, C-O), 10.29, 12.19, 14.05 and the like.

Mass spectral analysis of a silylated sample of the product showed maxima at m / e 462 and 457, a confirmation the presence of two carboxyl groups.

Example 9

1,4-dithiine / 2,3-c; 6,5-cj_7diisothiazole-3,7-dicarboxylic acid (Formula 1, R = -CO ₂ H)

0.28 g of 3,7-dicyan-1,4-dithiin / 2,3c; 6,5-c_Vdiisothiazole and 50 ml of concentrated hydrochloric acid were refluxed overnight. The resulting solution was cooled and poured on ice. The deep yellow solid dicarboxylic acid was filtered off. Your identity was through Infrared analysis confirmed.

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-M-

Example 10

1,4-dithiine / 2,3-c; 6,5-cj7diisothia2ol-3,7-dicarbonyl chloride (Formula 1, R = -COCl)

COCl

COCl

1 g (2.5 milliequivalents) of the dipotassium salt of 1,4-dithiine / 2,3-cj 6,5-cJ_7diisothiazole-3,7-dicarboxylic acid was acidified with 6N hydrochloric acid. The suspension was stirred for 30 minutes. The dicarboxylic acid formed as an intermediate was filtered off and mixed with 74 ml of thionyl chloride and 0.5 ml of dimethylformamide. The reaction mixture was refluxed for 6 hours and cooled to room temperature. Here was. the desired compound as an orange solid precipitated 236-237 ⁰ C of melting point.

Further analysis values were determined for a sample of the dicarbonyl chloride prepared in the same way.

Elemental analysis: Calculated for CgN Found:

UV (CH ₂ Cl ₂ ):

27.1

7.89
776T

36.1

Cl 20.0

^nm

³⁰¹ (9-380)

IR (KBr): 5.84 Cs, carbonyl), 6.84 (s, conjugated C «C and / or C = N), 7.45 (s), 7.55 (s), 7.75 (s), 7.85, 8.50, 10.13 (s), 10.54, 12, O6 (s), 14.2-14.3 (broad) u.

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Example 11

Ν, Ν, Ν ·, N ^f -tetramethyl-1,4-dithiyne / 2,3-c; 6,5-c_Vdiisothiazol-3,7-dicarboxamid (Formula 1, R = -CON (CH ₃ ) ₂ )

COCl

(CH,)

COCl. COH (CH.)

A mixture of 0.41 g 1,4-dithiine / 2,3-c; 6,5-cV diisothiazole dicarbonyl chloride and 80 ml of aqueous dimethylamine was stirred at room temperature for 30 minutes. That Crude product was filtered off and recrystallized from chlorobutane to give the desired compound as pale yellow solid of melting point 218-220.5 ° C was obtained.

Elemental analysis: £ iH H iL

Calculated for ^C ₁₂ ^H 12 ^N 4 ° 2 ^S 4 ^{: 38} ' ^{7 3} ' ^{25 15} '° ³⁴ » ⁴ Found: 1% 1 37Ö8 TiT? 3--74

IR (KBr): 2.93 (b, se k. Amide), 3.43, 6.16 (s, carbonyl), β.71, 6.98, 7.20 7.80 (a), 7.94, 8.45, 9.14, 9.40, 10.34, IO.83, 11.40, 13.38, 14.99 y.

UV (CH ₂ Cl ₂ ): X _max 309 nm (elO _f 81 6).

A solution of the dicarboxamide in ether became fluorescent when irradiated with ultraviolet light. the Use of the dicarboxamide as a fluorescent brightener was illustrated as follows: A multi-ply swatch was immersed in an aqueous suspension of the dicarboxamide, whereupon the suspension for 30 minutes 100 ° C was heated. The sample was taken from the suspension, rinsed well with distilled water and

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dries. The dried sample was placed under UV light examined using an untreated comparative sample. All fabric layers of the sample showed fluorescence.

If the dimethylamine is replaced by the amines mentioned below, the corresponding dicarboxamides become obtained: methylamine, ethylamine, n-propylamine, n-butylamine, n- ^ entylamine, isopropylamine, sec-butylamine, Diethylamine, 2-pentylamine, N-methyl-1-propylamine, N-ethyl-1-propylamine, diisopropylamine, N-methyl-1- ' butylamine, N-propyl-1-butylamine, 3-pentylamine, N-propyl-1-pentylamine, N-methyl-3-pentylamine and ammonia.

Example 12

Dimethyl 1,4-dithiyne / 2,3-cj 6,5-c ^ / diisothiazole-3,7-dicarboxylate (Formula 1, R = -

COCl

CO "CIL

CILOH / pyridine

COCl

CO ₂ CH,

Total 2g (5.6 milliequivalents) 1,4-dithiine / 2,3-c; 6, 5-cJ_ / diisothiazol-3, 7-dicarbonyl chloride was used under Stirring at room temperature under nitrogen to a mixture of 25 ml of methanol and 25 ml of pyridine. The suspension was stirred for a further 2.5 hours. The crude solid product was separated and washed with water and Washed dilute hydrochloric acid to give 2.13 g of the crude ester. By recrystallization twice the desired compound with a melting point of 240 ° -243 ° C. was obtained in pure form from chlorobutane.

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E learn tar analysis: £ ü H JL

Calculated for C ₁₀ HgN ₂ S ₄ O ₄ : 34.7 1.75 8.09 37.0

Found: 35.0 1.94 '8.04

UV (CH ₂ Cl ₂ ): X _max 372 nm (£ 12,110), 280 (6055).

When using the alcohols listed below in place of methanol, the corresponding dicarboxylates are obtained: 1-propanol, 2-propanol, 1-butanol, sec-butanol, isobutyl alcohol, t ^B utylalkohol, 1-penta nol, 2-pentanol, 3 -Pentanol, 3-methyl-2-butanol and 3-methyl-3-butanol.

Example 13

Diethyl 1,4-dithiine / 2,3-c; 6,5-cV "diisothiazole-3,7-dicarboxylate (Formula 1, R =

When using ethanol instead of methanol in the experiment described in Example 12, the desired Compound obtained from melting point 191-193 ° C.

Example 14

Dibenzyl-1,4-dithiine / 2,3-cj 6,5-cj_7diisothiazol-3,7-dicarboxylate (Formula 1, R = -CO ₂ CH ₂ CgH ₅ )

When using benzyl alcohol instead of methanol in the experiment described in Example 12, the desired compound with a melting point of 245 ° C.

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- 18 -

Example 15

N, N'-bis (4-methoxypheny1) -1,4-dithiyne / 2,3-c; 6.5-cV7
diisothiazole-3,7-dicarboxamide (Formula 1, R = 4-CH ₃ OC
NHCO-)

COCl

+ 2 HaN-r 'V-OCH ₃

COCl

CH ₃ O

A mixture of 2.0 g (5.6 millimoles) 1,4-dithiin / 2,3-c,
ö ^ -cVdiisothiazole-S ^ -dicarbonyl chloride, 3.0 gj (23.6 mmol) of 97% p-anisidine and 60 ml of 1,2-dichloro-1 ethane was heated on the reflux condenser. During the _; Additional solvent was added to the reaction while a yellow solid precipitated. After 2 hours. The mixture was cooled by heating on the reflux condenser,
filtered and washed successively with 1,2-dichloroethane, water, 2B alcohol and ether, with 2.895 g (5.48 "; mmol, 98%) of a yellow solid product with a
Melting point of about 330 ° C were obtained. Ujticrystallization of this product from Ν, Ν-dimethylformamide (DMF) (about 70 ml) provided the desired compound
obtained in pure form with a melting point of 336-339 ° C.
Elemental analysis; . C_ £ JN &

Calculated for ^C ₂ 2 ^H 16 ^N 4 ^S 4 ° 4 ^: 49.98 3.05 10.60 24.26

Found: 50.09 3.28 10.64 24.44

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If the amines mentioned below are used instead of p-anisidine, the corresponding dicarboxamides which have the structures and names given in Examples 16 to 20 below.

Dicarboxa mide made from aromatic amines

example

Amine product of formula I

Melting point of the product

16

p-nitroaniline R

17th

p-toluidine

18th

o-nitroaniline

19th

N-methyl-p-nitroaniline

20th

N-methyl-onitroaniline 4-O ₂ NC ₆ H ₄ NHCO-

N, N -Bi s (4-ni tro £ heny 1) 1,4-di thiine / _2, 3-c; 6,5-cJVdiisothiazole-3,7-dicarboxamide

R = 4-CH ₃ C ₆ H ₄ NHCO-N, N'-bis (4-tolyl) -1, 4-dithiyne / 2 ~, 3-cj 6,5-c_I_ / diisothiazole-3,7-dicarboxamide

R = 2-O ₂ NC ₆ H ₄ NHCO-

> 37O ° C (decomp.)

353-355 ⁰ C

350-353 ⁰ C

N, N · -Bis (2-nitrophenyl) -l, 4-dithiyne / 2,3-c} 6,5-cVdiisothiazole-3,7-dicarboxamide

R β CO- -> 35O ° C (decomp.)

N, N'-bis (4-nitropheny1) -N, N'-dimethyll, 4-di ^ hiin / 2,3-c; 6 ₇ 5-c ^ / diIsothiazole-3,7-dicarboxamide

R * 2-0 ₅ NC _fi H ,, N-CO- ^{ά b} . *

> 35O ° C (decomp.)

N, N «-Bis (2-nitrophenyl) .- N ₁ N ¹ -dimethyl-1,4-dithiyne / 2,3-c; 6,5-cj7-diisothiazole-3,7-diarboxamide.

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Example 21

3, 7-dicyano-1,4-dithiine / 2,3-c; 6,5-cVdiisothiazole (formula I ₁ R = -CN)

^{c = 0}

S, NaI

CH ₃ OCH ₂ CH ₂ OCH ₃

CN

The reaction was carried out under nitrogen in a flask equipped with a reflux condenser and a stirrer. 500 ml of 1,2-dimethoxyethane was added to the flask under nitrogen, followed by the addition of 60 g (1.875 equivalents) of sulfur and 20 g of sodium iodide (dried over refluxing benzene). The mixture was refluxed with stirring for 0.5 to 1 hour (& 3-84 ° C) until a clear yellow solution had formed. The mixture was cooled to about 50 ⁰ C and treated with 25 g (0.149 mol) of 4,5-dicyano-l, 3-dithiols-2-one (prepared by the method of US-PS 3,140,295 and recrystallized from benzene) treated . The mixture was stirred and refluxed for 18 hours (83%)

wet

up to 84 ° C), then ^{cooled to 0 0} C CEis / acetone) and filtered. The solid residue product was washed with water and carbon disulfide to remove inorganic salts and sulfur and dried. The yield was 11.06 "g (0.039 mol, 53%); melting point 280 ° C. When mixed with a sample of the same product which had been prepared by the method described in Example 1, the product showed no reduction in melting point.

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Example 22
Bi s (te tr abu ty 1 ammon ium) -1,4-di thi in / ^ 2,3-c; 6,5-cV-diisothiazole-3,7-dicarboxylate
(Formula I, R = - ^{- +}

CO ₂ H

J ⁺ OH "

CO ₂ H

1.6 g (5.0 millimoles) 1,4-dithiine / 2,3-c; 6,5-cVdiisothiazole-3,7-dicarboxylic acid (Examples 9 and 10) were in 12 ml (12 mmol) of 1 molar hot methanolic tetrabutylammonium hydroxide solution solved. The methanol was evaporated and the viscous oily residue with tetrahydrofuran triturated and filtered to give 3.276 g of crystalline product. This product was recrystallized from a mixture of acetonitrile, tetrahydrofuran and ethyl acetate and from acetone, wherein 1.846 g of the desired compound having a melting point of 167-169 ° C. were obtained.

Elemental analysis; £ ü H JL

Calculated for ^c ₄₀ ^H 72 ^N 4 ^S 4 ° 4 ^: 59.95 9.06 6.99 16.01

Found: 59.64 8.92 7.31 15.88

59.89 9.10 7.41 15.72

The compounds according to the invention have a wide variety of uses. The dinitrile serves as the starting and intermediate for the other compounds according to the invention having their own uses to have. For example, the dipotassium salt of 1,4-dithi in / 2, 3-c; öjS-cV / diisothiazole-S ^ -dicarboxylic acid as a pH indicator.

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Example A.

A range of buffer solutions with pH values from 1 to IO was produced. A piece of filter paper was refluxed for 30 minutes in a suspension of the dipotassium salt of 1,4-dithiine / 2 ~, 3.c; 6,5-cVdiisothiazole-3,7-dicarboxylic acid (2.0 g) heated in 60 to 80 ml of water. The paper was dried and cut into strips. The strips were immersed in the various buffer solutions. The gradual change in color of the stripes with Increasing pH, as shown in the following table, illustrates that salt is a useful indicator for acidity is.

pH color of the paper

1 Intense yellow 2 yellow 3 pale yellow 4th very pale yellow, almost colorless 7th colorless 10 colorless

The dicarboxylic acid is suitable as a fluorescent agent and as a dye.

Example B.

An aqueous suspension of 2.0 g of the dipotassium salt of 1,4-dithiine / 2 ~, 3-c; 6,5-c_V / diisothiazole-3,7-dicarboxylic acid in 60 to 80 ml of water was heated to the reflux temperature. A fabric sample consisting of various threads was placed in the suspension. Then ^; was heated for a further hour and the fabric sample ■ removed, rinsed with cold water and dried. The cotton and viscose rayon parts of the fabric sample showed fluorescence when exposed to ultraviolet light.

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The swatch was acidified in dilute acetic acid solution. All the fibers turned yellow, and the nylon, The silk and acetate parts of the swatch fluoresced intense when exposed to ultraviolet light.

The dicarboxylic acid chloride according to the invention is particularly advantageous for the production of fluorescent Polyamides. The dicarboxylic acid chloride and the dicarboxylates are suitable components for manufacture of polyethers and polyester glycols, which are suitable for the production of polyester and polyurethane resins are.

Example C

A suspension of 2.0 g (5.6 milliequivalents) 1,4-dithiin / 2,3-c; 6,5-cj_7diisothiazol-3, 7-dicarbonyl chloride 200 ml of dry methylene chloride was quickly placed in a jacketed mixer cooled with ice water given, the 0.75 g (6.6 milliequivalents) trans-2,5-dimethylpiperazine, 200 ml of water, 11.27 ml of aqueous sodium hydroxide solution and 31 ml of methylene chloride ent held. The suspension was stirred rapidly for 30 minutes (pH 10). The methylene chloride was reduced under Pressure removed and the crude polymer filtered off, washed with acetone and water and dried, whereby 2.25 g of pale yellow polyamide was obtained.

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JLC-

The polyamide was fractionated with chloroform to form two fractions, one in chloroform insoluble fraction (A) and a fraction (B) soluble in chloroform.

A: 1.27 g of pale yellow granular solid, decomposition at 335-36O ° C., inherent viscosity If _{1 h} 0.88 (0.1% solution in concentrated HpSO., 25 ° C.).

B: 0.42 g, light yellow / orange solid, decomposition at 318 ° C., inherent viscosity 0.07 (0.1% solution in concentrated HpSO ₄ at 25 ° C.).

The two products A and B fluoresced in the solid Condition when exposed to UV light. Films of the two products A and B (made from methanesulfonic acid) also showed Fluorescence. ·

By solution polymerization (in dimethylacetamide) of 1,4-dithiine / 2,3-c; 6, S-cS / diisothiazole-S, 7-dicarbonyl chloride with trans-2,5-dimethylpiperazine, a polyamide was also obtained which, when exposed to UV light fluoresced.

Example D

-NH

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By solution polymerization of 1,4-dithiin £ 2,3-c; 6,5-cJ_7diisothiazole-3,7-dicarbonyl chloride (2.0 g, 5.6 Milliequivalent) with p-phenylenediamine (0.61 g, 5.6 milliequivalent) in 100 ml of hexamethylphosphoramide (HMPA) a polyamide was obtained that was fractionated, whereby an HMPA-insoluble fraction (A) and an HMPA-soluble fraction (B) were obtained. The parliamentary group B was precipitated by adding water.

A: 0.33 g, decomposition at 350 ° C., inherent viscosity 0.119 (0.1% strength solution in concentrated H ₃ SO ₄ at 25 ° C.).

B: decomposition at 222 ° C.

The two fractions A and B showed fluorescence in the solid state when exposed to UV light. Slides from the both products A and B (from methanesulfonic acid) also showed fluorescence.

Example E.

A dispersion (absolutely covering color) of 1 g 1,4-dithiine / 2,3-c; 6,5-c_Vdiisothiazole-3,7-dicarboxylic acid and 1 gram of clearcoat was prepared by rolling the mixture ten times on a Hoover pan mill. One A 1:30 dilution of this dispersion was made by adding 0.175 g of the dispersion and 5 g of a 3.2: 1 zinc oxide lacquer paste were mixed with a spatula · Both the dispersion with absolutely opaque color and the stretched dispersion were drawn out into thin films in sized paper and used for determinations of the Color and lightfastness used.

The colors of the films are identified by the Munsell indices ("Munsell Book of Color", Munsell Color Company, Inc., Baltimore, Maryland, 1966): 7.5Y 8.5 / 12 for

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the absolutely opaque color and 6Y 8.5 / 10 for the dispersion stretched in a ratio of 1:30. Generally said the color is a bright primrose yellow.

Lightfastness

After 2 hours of treatment, the fade meter (type FDA-R, Atlas Electric Devices Co., Chicago), the films from the dispersion showed with absolutely solid color and from the stretched dispersion a barely perceptible change in the color> change.

Chemical resistance

Test panels were produced by grinding the dry pigment with alkyd resin 30J as binder in a pigment / binder ratio of 0.5 and the test panels sprayed and the film was baked for 30 minutes at 121 ° C. 4% aqueous solutions were applied to a painted test panel Solutions of hydrochloric acid, sulfuric acid, sodium hydroxide and sodium sulfide are applied. The test board was heated to 60 ° C for 30 minutes. It showed good resistance to the four solutions.

Get lost

A strip of the paint consisting of TiOp and 30J alkyd resin was sprayed onto one of the pigment panels. After 30 minutes at 121 ^° C., no sign of undressing was found.

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Claims (10)

Diisothiazole claims of the formula wherein the two radicals R are the same and are -H, -CN, -COCl, -CO ₂ R ¹ , -CONR ² R ³ or -CO ₂ "" (alkyl) ₄ N ⁺ , R ^{1 is} -H, alkyl with 1 to 5 carbon atoms, phenyl or benzyl and R ² and R ³ stand for —H, alkyl having 1 to 5 carbon atoms, phenyl or a phenyl radical substituted by alkyl radicals, alkoxy radicals, nitro groups, halogen atoms or dialky / amino groups, the alkyl radical containing 1 to 5 carbon atoms. 2) S ^ -dicyan-l ^ -dithiin / ä ^ -c; 6,5-c_Vdiisothiazole. 3) 1,4-dithiine / 2,3-c; 6,5-cVdiisothiazole. 4) 1,4-dithiine / 2,3-c; 6,5-cJ_7diisothiazole-3,7-dicarboxylic acid 5) 1,4-dithiine / 2,3-c; 6,5-cJ_7diisothiazol-3, 7-dicarbonylchloride 6) N, N, N ', N'-tetramethyl-1,4-dithiyne / 2,3-c; 6,5-cVdiisothiazole-3,7-dicarboxamide. 7) dimethyl-1,4-dithiine / 2,3-c; 6,5-c_Vdiisothiazole-3,7-dicarboxylate. 8) Process for the preparation of compounds according to claim 1 to 7, characterized in that one tetracyane-1,4-dithiin or 4,5-dicyan-1,3-dithiolen-2-one with sulfur in 1,2-dimethoxyethane at one temperature brings together from about 50 to 280 ° C in the presence of a basic catalyst, and converts. 709817/1072 ORIGINAL INSPECTED 9) A method according to claim 8, characterized in that it is carried out at a temperature in the range of about 75 ° to 85 ⁰ C. 10) Process according to claim 8 and 9, characterized in that the basic catalyst used is an alkali iodide or a tertiary aliphatic amine is used. 70 9 817/107 2