CH411906A - Process for the preparation of new 1,3,4-thiadiazoles - Google Patents

Description

  

  



  Process for the production of new 1, 3, 4-thiadiazoles
The present invention relates to a process for the preparation of new 1, 3, 4-thiadazoles which have the formula
EMI1.1
 in which R ", R2 and Rs are aromatic or heterocyclic radicals, at least one of these radicals being heterocyclic, and n being an integer of at most 2.



   The inventive method for preparing the new thiadiazoles of the formula (1) consists in that one acylhydrazines of the formula
EMI1.2
 where R1, R2, Rs and n have the meaning given, reacts with phosphorus sulfides.



   The acylhydrazines used as starting materials are derived from hydrazine and heterocyclic and optionally aromatic monocarboxylic acids, acylhydrazines with two hydrazine radicals (n = 2) also from heterocyclic or optionally aromatic dicarboxylic acids. In particular, those heterocyclic monocarboxylic acids which result in the radical Ri and / or R2 and contain a single) ring are suitable, e.g.

   B. a five- to six-membered ring with preferably a single heteroatom (N, O, S) and 2 or 3 ring double bonds. Among the aromatic monocarboxylic acids to be emphasized are those which, like benzene, diphenyl and naphthalenecarboxylic acids, contain 1 to 2 aromatic rings. Among the aromatic dicarboxylic acids, benzene dicarboxylic acids are particularly suitable.



   All of the carboxylic acids used to prepare the acylhydrazines, but especially the monocarboxylic acids of the benzene series, can also have other, preferably non-cyclic, substituents, eg. B. halogen atoms such as bromine or chlorine, alkyl groups such as methyl, ethyl, n-propyl, isopropyl, tert. Butyl, alkoxy groups such as methoxy or ethoxy.



   From the above information it can be seen that the starting materials used are preferably those acylhydrazines of the formula (2) in which Ri, R2 and Rs are aromatic radicals containing 1 to 2 aromatic six-membered rings or heterocyclic radicals with a single, five- to six-membered hetero ring and at least one of Ri, R2 and R3 is hetero cycMscb. Thus, in the acylhydrazines of the formula (2), for.

   B. R1 and R2 benzene, diphenyl, naphthalene, pyridine, furan or thiophen radicals and R2 a benzene, furan or thiophene radical, but at least one of these radicals is heberocyclic.



  The preferred constitution of the thiadiazoles of the formula (1) results from the above information.



     The dialylhydrazines of the formula (2) with a single hydrazine radical (n = 1) can advantageously be prepared by diacylating hydrazine hydrate or a suitable hydrazine salt, such as hydrazine sulfate, with a halide, preferably the chloride, a heterocyclic monocarboxylic acid, or by diacylating such a hydrazine compound first monoacylated with an ester monocarboxylic acid and the monoacylhydrazine further acylated with a halide of another monocarboxylic acid, the derivatives of two different heterocyclic monocarboxylic acids or a derivative of a heterocyclic and an aromatic monocarboxylic acid being used.

   In this way, symmetrical diacylhydrazines are obtained in the first case and asymmetrical diacylhydrazines in the second.



   Acylhydrazines of the formula (2) with two hydrazine radicals (n = 2) are obtained if hydrazine is acylated with dicarboxylic acid esters on the one hand and with monocarboxylic acid halides in a molar ratio of 2: 1: 2. For example, 2 moles of hydrazine with 1 mole of a dicarboxylic acid derivative can be converted into a compound of the formula
EMI2.1
 convert and further acylate the two H2N groups of this compound with 2 moles of a single monocarboxylic acid halide or with 1 mole each of two different monocarboxylic acid halides. Here too, of course, the starting materials are to be selected so that the acyl compounds obtained correspond to the formula (2).



   The following may be mentioned as monocarboxylic acids whose halides and / or esters can be used for the preparation of the acylhydrazines of the formula (2):
Benzene carboxylic acids of the formula
EMI2.2
 wherein X is a hydrogen atom, an alkyl group with 1 to 4 carbon atoms, an alkoxy group with 1 to 4 carbon atoms, a halogen atom, such as bromine or preferably chlorine, or a phonyl radical, such as 2-, 3- or 4-methylbenzene carboxylic acid, 2-, 3 -or 4-chlorobenzenecarboxylic acid, 2-, 3- or 4-bromobenzenecarboxylic acid, 4-tert.

     Butylbenzenecarboxylic acid, 2,4-dimethylbenzenecarboxylic acid, 3, 4-dimethylbenzenecarboxylic acid, 3, 5-dimethylbenzenecarboxylic acid, 2, 4-dichlorobenzenecarboxylic acid, 3, 4-dichlorobenzenecarboxylic acid, 2-, 3- or 4-methoxybenzenecarboxylic acid, 2, 4-, 2, 2, 4-, 2, 2, 4-dichlorobenzenecarboxylic acid, -or 3, 4-Dimethoxybenzenecarboxylic acid, 2, 4, 5- or 3, 4, 5-trimethoxybenzenecarboxylic acid, 2-, 3- or 4-thoxybenzenecarboxylic acid, 2-methoxy-4- or 5-methylbenzenecarboxylic acid, 2-methoxy 5-chlorobenzenecarboxylic acid, 2-ethoxy-4-methylbenzenecarboxylic acid, diphenyl-4-carboxylic acid;
Naphthalenecarboxylic acids, such as naphthalene-1 or 2-carboxylic acid, 3-methoxynaphthalene-2-carboxylic acid;

  
PyridincarbonsÏuren, such as pyridine-2 -, - 3-or-4-carboxylic acid; Furan carboxylic acids, such as furan-2-carboxylic acid, 3, 4-dichlorofuran-2-carboxylic acid, 5-chlorofuran-2-carboxylic acid; Thiophene carboxylic acids, such as thiophene-2-carboxylic acid, 3- or 5-methylthiophene-2-carboxylic acid, 3,5-dimethyl-thiophene-2-carboxylic acid, 5-chlorothiophene-2-carboxylic acid.



   Dicarboxylic acids, the halides of which can be used to prepare acylhydrazines with two hydrazine residues, include: isophthalic acid, terephthalic acid, 1,1'-diphenyl-4, 4'-dicarboxylic acid, furan-2, 5-dicarboxylic acids, thiophene-2, 5- dicarboxylic acid, 3, 4-dimethyl-thiophene-2, 5-dicarboxylic acid.



   Phosphorus sulfides for the preparation of the thiadiazoles include phosphorus heptasulfide (P4S,), phosphorusquisulfide (P4S3), phosphorus trisulfide (P3S3) and preferably phosphorus pentasulfide (PaS,).



   The reaction is preferably carried out in the presence of a tertiary nitrogen base. It is advisable to use tertiary nitrogen bases with a boiling point that is not too low, preferably those whose boiling point is at least 100, such as. B.



     N, N-diethyl or N, N-dimethylaniline. Cyclic tertiary nitrogen bases such as quinoline and especially pyridine bases such as pyridine itself and alkyl pyridines with low molecular weight alkyl radicals such as 2-, 3- and 4-methylpyridine (picolines), ethylpyridines, or mixtures of such pyridine bases prove to be particularly advantageous.



   The reaction is expediently carried out in such a way that one uses a clear excess of phosphorus sulfide over the theoretically minimal amount of 2 atoms of sulfur required to form a thiadiazole ring and at least enough l of the tertiary nitrogen base that the reaction mixture initially becomes a solution or at least forms an easily agile suspension. In general, the reaction is rather strongly exothermic. It is therefore advisable to gradually add the phosphorus sulfide to the solution of the acylhydrazine in the tertiary base at room temperature and to begin with the external supply of heat only when the reaction mixture is after the addition of the phosphorus sulfide no longer self-heated.



  To terminate the reaction, the mixture is advantageously for a few hours at elevated temperature, e.g. B. held between 80 uod 150, the resulting thiadiazole generally begins to deposit. After the reaction has ended, the separation can be completed by adding water and, if desired, water-soluble organic solvents.



   It is also possible to prepare the acylhydrazines required as starting materials in the present process from carboxylic acid halides and hydrazine compounds in the presence of a tertiary nitrogen base and to react the acylhydrazines thus obtained with phosphorus sulfides without intermediate separation. For example, in a tertiary nitrogen base, preferably a pyridine base, a symmetrical or preferably asymmetrical diacylhydrazine can be produced from a monoacylhydrazine by means of a carboxylic acid halide and the reaction with the phosphorus sulfide can then be carried out immediately.



   The new thiadiazoles can still be implemented. For example, they can be sulfonated, nitrated or chlorinated. Basic compounds with tertiary nitrogen atoms, e.g. B. those with pyridine rings can also be quaternized.



   The new thiadiazoles can z. They can be used, for example, as protective agents against ultraviolet radiation, as optical brighteners, as scintillators, for electrophotographic reproduction or as intermediates in the manufacture of dyes.



   In the following examples, unless otherwise noted, the parts are parts by weight, the percentages are percentages by weight, and the temperatures are given in degrees Celsius.



   example 1
24.1 part of N-benzoyl-N'-isonicotinylhydrazine are mixed in 150 parts by volume of pyridine with 30 parts of phosphorus pentasulphide while stirring, the reaction mixture heating up. As soon as the exothermic reaction has subsided, the temperature is brought to 60 to 65 in the course of 30 minutes.



  The mixture is stirred for one hour at 60 to 65, the temperature is increased over the course of an hour to reflux and: the reaction mixture is stirred at a low boiling point for 15 hours. The mixture is cooled to room temperature, 50 parts by volume of ethanol, then 2500 parts of ice water are added in several portions and the mixture is neutralized with aqueous sodium hydroxide solution. The 2- [pyridyl- (4 ')] - 5-phenyl-1, 3, 4-thiadiazole of the formula
EMI3.1
 is sucked, washed with 2000 parts of cold water and dried. About 20.6 parts, corresponding to 86.2% of theory, are obtained, colorless, glossy platelets which melt at 182 to 183¯.



  Recrystallization three times from ethanol-water (2: 1) gives about 9.8 parts, corresponding to 41% of theory, colorless, shiny platelets which melt at 182 to 183.2 and fluoresce very weakly blue under ultraviolet light.



  Analysis: ClsH9NsS (239, 29) calculated: C 65, 25 H 3, 79 N 17, 56 found: C 65, 01 H 3, 80 N 17, 48.



     UV absorption in dioxane:? Max = 302 mÁ (? = 21400).



   The table below describes a further 1, 3, 4 thiadiazole compounds which can be prepared according to the above procedure. The information on the yield relates to the crude product. The abbreviations in the column above the fluorescence mean the following:
SS very weak
S: weak
M: medium
St: sbark
L: luminous
H: bright
W: white
O orange
G: yellow
Countess
B:

   blue
V purple
EMI3.2


<tb> No. <SEP> Formula <SEP> Off properties <SEP> Analysis <SEP> / e
<tb> <SEP> loot <SEP> calculated <SEP> found
<tb> <SEP> in <SEP> ouzo <SEP> (Mol) <SEP> fluorescence
<tb> <SEP> CHs <SEP> 79, <SEP> 9 <SEP> Colorless, <SEP> very <SEP> C <SEP> 66, <SEP> 38 <SEP> C <SEP> 66, <SEP> 23 <SEP> 307 <SEP>! <SEP> 20400
<tb> <SEP> S, <SEP> fine, <SEP> matted <SEP> H <SEP> 4, <SEP> 38 <SEP> H <SEP> 4, <SEP> 52 <SEP> 241/2300
<tb> <SEP> 6 <SEP> NG <¯C <SEP> C <<SEP> little needle <SEP> N <SEP> 16, <SEP> 59 <SEP> N <SEP> 16, <SEP> 64 < SEP> SS-B
<tb> <SEP> in <SEP> F = 141, <SEP> 8-143, <SEP> 2 <SEP> (253, <SEP> 31)
<tb> <SEP> (ethanol-water
<tb> <SEP> 5 <SEP>:

   <SEP> 2)
<tb> <SEP> S <SEP> 74, <SEP> 3 <SEP> Small, <SEP> colorless, <SEP> C <SEP> 66, <SEP> 38 <SEP> C <SEP> 66, <SEP > 36 <SEP> 310 <SEP>! <SEP> 22800
<tb> <SEP> \ /// - \\ - glkzenide <SEP> H <SEP> 4, <SEP> 38 <SEP> H <SEP> 4, <SEP> 54 <SEP> SS-B
<tb> <SEP> II <SEP> II <SEP> plate <SEP> N <SEP> 16, <SEP> 59 <SEP> N <SEP> 16, <SEP> 75
<tb> <SEP> N-N <SEP> and <SEP> needles <SEP> (253, <SEP> 31)
<tb> <SEP> F = 167-168, <SEP> 6
<tb> <SEP> (ethanol-water
<tb> <SEP> 5 <SEP>:

   <SEP> 2)
<tb>
EMI4.1


<tb> No. <SEP> Formula <SEP> Off properties <SEP> Analysis <SEP> Amax
<tb> <SEP> loot <SEP> calculated <SEP> found <SEP> max
<tb> <SEP> in <SEP> ouzo <SEP> (Mol) <SEP> fluorescence
<tb> <SEP> CHUS <SEP> 76, <SEP> 9 <SEP> Colorless, <SEP> very <SEP> C <SEP> 69, <SEP> 12 <SEP> C <SEP> 69, <SEP> 02 <SEP> 312 <SEP>! <SEP> 24800
<tb> <SEP> ", // - \\ <SEP> I <SEP> fine <SEP> Nii-delchen <SEP> H <SEP> 5, <SEP> 80 <SEP> H <SEP> 5, < SEP> 72 <SEP> SS-B
<tb> <SEP> II <SEP> II <SEP> I <SEP> F = 167-168, <SEP> 5 <SEP> N <SEP> 14, <SEP> 23 <SEP> N <SEP> 14, <SEP> 33
<tb> <SEP> N-N <SEP> (ethanol-water <SEP> (295, <SEP> 41)
<tb> <SEP> 2 <SEP>:

   <SEP> 1)
<tb> <SEP> CH3 <SEP> 80, <SEP> 2 <SEP> Colorless, <SEP> very <SEP> C <SEP> 67, <SEP> 39 <SEP> C <SEP> 67, <SEP> 28 <SEP> 316/22500
<tb> <SEP> fine, <SEP> glossy <SEP> H <SEP> 4, <SEP> 90 <SEP> H <SEP> 5, <SEP> 21 <SEP> 242/5900
<tb> <SEP> 9 <SEP> N <SEP> C-CHs <SEP> little needles <SEP> N <SEP> 15, <SEP> 72 <SEP> N <SEP> 15, <SEP> 92 <SEP> St-B
<tb> <SEP> k / 11 <SEP>! <SEP> F '= 179, <SEP> 5-181, <SEP> 5 <SEP> (267, <SEP> 34)
<tb> <SEP> (ethanol-water
<tb> <SEP> 3 <SEP>:

   <SEP> 1)
<tb> <SEP> ci <SEP> 79, <SEP> 2 <SEP> Colorless, <SEP> very <SEP> C <SEP> 57, <SEP> 04 <SEP> C <SEP> 56, <SEP> 99 <SEP> 298/21600
<tb> <SEP> fine, <SEP> shiny <SEP> H <SEP> 2, <SEP> 95 <SEP> H <SEP> 2, <SEP> 97 <SEP> SS-B
<tb> 10 <SEP> NAC <SEP> C <<SEP> little needles <SEP> and <SEP> N <SEP> 15, <SEP> 35 <SEP> N <SEP> 15, <SEP> 10
<tb> <SEP> il <SEP> ii <SEP> plate <SEP> (273, <SEP> 75)
<tb> <SEP> F = <SEP> I48, <SEP> 2-150
<tb> <SEP> (ethanol-water
<tb> <SEP> 1 <SEP>:

   <SEP> 1)
<tb> <SEP> S <SEP> 62, <SEP> 1 <SEP> Colorless, <SEP> very <SEP> C <SEP> 57, <SEP> 04 <SEP> C <SEP> 56, <SEP> 93 <SEP> 309/24800
<tb> 11 <SEP> NC <SEP> C - \\ - ci <SEP> fine, <SEP> matted, <SEP> H <SEP> 2, <SEP> 95 <SEP> H <SEP> 2, < SEP> 94 <SEP> SB
<tb> <SEP> II <SEP> 11 <SEP> \ <SEP> shiny <SEP> N <SEP> 15, <SEP> 35 <SEP> N <SEP> 15, <SEP> 22
<tb> <SEP> N-N <SEP> little needle <SEP> (273, <SEP> 75)
<tb> <SEP> F = <SEP> 190, <SEP> 6-192
<tb> <SEP> (ethanol-water
<tb> <SEP> 5 <SEP>:

   <SEP> 2)
<tb> <SEP> S <SEP> 81, <SEP> 1 <SEP> Colorless, <SEP> fine, <SEP> C <SEP> 49, <SEP> 07 <SEP> C <SEP> 48, <SEP > 77 <SEP> 310/26800
<tb> 12 <SEP> matted <SEP> H <SEP> 2, <SEP> 53 <SEP> H <SEP> 2, <SEP> 63 <SEP> SS-B
<tb> <SEP> II <SEP> II <SEP> little needle <SEP> N <SEP> 13, <SEP> 21 <SEP> N <SEP> 13, <SEP> 04
<tb> <SEP> N-N <SEP> F = 222-223 <SEP> (318, <SEP> 21)
<tb> <SEP> (dioxane-ethanol
<tb> <SEP> water <SEP> 3 <SEP>: <SEP> 3 <SEP>:

   <SEP> 2)
<tb> <SEP> ci <SEP> 82, <SEP> 5 <SEP> Colorless, <SEP> very <SEP> C <SEP> 50, <SEP> 66 <SEP> C <SEP> 50, <SEP> 95 <SEP> 310/24200
<tb> <SEP> fine, <SEP> matted <SEP> H <SEP> 2, <SEP> 29 <SEP> H <SEP> 2, <SEP> 25 <SEP> 302/24400
<tb> 13 <SEP> \\ - Cl <SEP> Nddelchen <SEP> N <SEP> 13, <SEP> 64 <SEP> N <SEP> 13, <SEP> 39 <SEP> S-B
<tb> <SEP> ii <SEP> ii <SEP> F = 173-174, <SEP> 6 <SEP> (308, <SEP> 20)
<tb> <SEP> (ethanol-dioxane
<tb> <SEP> water <SEP> 2 <SEP>: <SEP> 1 <SEP>:

   <SEP> 1)
<tb> <SEP> OCHs <SEP> 92, <SEP> 2 <SEP> Almost <SEP> colorless, <SEP> C <SEP> 62, <SEP> 43 <SEP> C <SEP> 62, <SEP> 54 <SEP> 327/19800
<tb> <SEP> very <SEP> fine, <SEP> ver-H <SEP> 4, <SEP> 12 <SEP> H <SEP> 4, <SEP> 25 <SEP> 300/17000
<tb> 14 <SEP> N <SEP> C <SEP> C <SEP> felted needles <SEP> N <SEP> 15, <SEP> 60 <SEP> N <SEP> 15, <SEP> 59 <SEP> St -WV
<tb> <SEP> N-N <SEP> F = 143-144 <SEP> (269, <SEP> 33)
<tb> <SEP> (water-ethanol
<tb> <SEP> 4 <SEP>:

   <SEP> 1)
<tb> <SEP> OCH3 <SEP> 77, <SEP> 7 <SEP> Colorless, <SEP> very <SEP> C <SEP> 62, <SEP> 43 <SEP> C <SEP> 62, <SEP> 55 <SEP> 302/21900
<tb> <SEP> fine, <SEP> matted <SEP> H <SEP> 4, <SEP> 12 <SEP> H <SEP> 3, <SEP> 97 <SEP> M-B
<tb> 15 <SEP> N <SEP> c-Nlidelchen <SEP> N <SEP> 15, <SEP> 60 <SEP> N <SEP> 15, <SEP> 72
<tb> <SEP> F = 119, <SEP> 6-121, <SEP> 4 <SEP> (269, <SEP> 33)
<tb> <SEP> (Athanal <SEP> water
<tb> <SEP> 5 <SEP>:

   <SEP> 2)
<tb> <SEP> S \ <SEP> 82, <SEP> 8 <SEP> colorless, <SEP> fine, <SEP> C <SEP> 62, <SEP> 43 <SEP> C <SEP> 62, < SEP> 69 <SEP> 325/24600
<tb> 16 <SEP> NnC <SEP> C <<SEP> OCHs <SEP> matted, <SEP> glossyW <SEP> H <SEP> 4, <SEP> 12 <SEP> H <SEP> 4, <SEP > 13 <SEP> LB
<tb> <SEP> 11 <SEP> 11 <SEP> end <SEP> needles <SEP> N <SEP> 15, <SEP> 60 <SEP> N <SEP> 15, <SEP> 79
<tb> <SEP> N-N <SEP> F = 166, <SEP> 2-167, <SEP> 4 <SEP> (269, <SEP> 33)
<tb> <SEP> (ethanol-water
<tb> <SEP> 3 <SEP>:

   <SEP> 1)
<tb>
EMI5.1


<tb> No. <SEP> Formula <SEP> Off properties <SEP> Analysis
<tb> <SEP> loot <SEP> calculated <SEP> found
<tb> <SEP> in <SEP> / o <SEP> (Mol) <SEP> fluorescence
<tb> <SEP> OCHs <SEP> 67 <SEP> Colorless, <SEP> very <SEP> C <SEP> 63, <SEP> 58 <SEP> C <SEP> 63, <SEP> 63 <SEP> 329 / 23000
<tb> <SEP> kil, <SEP> I <SEP> small, <SEP> shiny <SEP> H <SEP> 4, <SEP> 62 <SEP> H <SEP> 4, <SEP> 50 <SEP> 304/16400
<tb> 17 <SEP> N <SEP> -C <SEP> C- <SEP> -CHsNädelchen <SEP> N14, <SEP> 83 <SEP> N <SEP> 15, <SEP> 07 <SEP> L-B
<tb> <SEP> ii <SEP> ii <SEP> F = 185-186, <SEP> 5 '<SEP> (283, <SEP> 34)
<tb> <SEP> N-N
<tb> <SEP> N-N <SEP> (ethanol-water
<tb> <SEP> 7 <SEP>:

   <SEP> 1)
<tb> <SEP> OCH3 <SEP> 67 <SEP> Colorless, <SEP> fine, <SEP> C <SEP> 63, <SEP> 58 <SEP> C <SEP> 63, <SEP> 27 <SEP> 335/16800
<tb> S <SEP>! -. <SEP> matted <SEP> H <SEP> 4, <SEP> 62 <SEP> H <SEP> 4, <SEP> 74 <SEP> 297/16200
<tb> <SEP> Needle <SEP> N <SEP> 14, <SEP> 83 <SEP> N <SEP> 14, <SEP> 81 <SEP> L-B
<tb> <SEP> N-N <SEP> I <SEP> F = 194-195 <SEP> (283, <SEP> 34)
<tb> <SEP> (ethanol-water
<tb> <SEP> 2 <SEP>:

   <SEP> 1)
<tb> <SEP> OCH3 <SEP> 56, <SEP> 7 <SEP> pale yellow, <SEP> glossy-C <SEP> 55, <SEP> 35 <SEP> C <SEP> 55, <SEP> 46 < SEP> 334/16600
<tb> S <SEP> I <SEP> nde <SEP> little needle <SEP> H <SEP> 3, <SEP> 32 <SEP> H <SEP> 3, <SEP> 45 <SEP> 294/17400
<tb> <SEP> 19 <SEP> 1C <SEP> C <<SEP> F = 210, <SEP> 4-212, <SEP> 2 <SEP> N <SEP> 13, <SEP> 83 <SEP> N <SEP> 13, <SEP> 60 <SEP> SS-WB
<tb> <SEP> N-N <SEP> I <SEP> (Dioxan-Athanl- <SEP> (303, <SEP> 78)
<tb> <SEP> N <SEP> N <SEP> water <SEP> 2 <SEP>: <SEP> 1 <SEP>:

   <SEP> 1)
<tb> <SEP> OCHs <SEP> 67, <SEP> 2 <SEP> Almost <SEP> colorless, <SEP> C <SEP> 60, <SEP> 18 <SEP> C <SEP> 60, <SEP> 23 <SEP> 336/27000
<tb> <SEP> S <SEP> \ <SEP> very <SEP> fine <SEP> H <SEP> 4, <SEP> 38 <SEP> H <SEP> 4, <SEP> 44 <SEP> L- HB
<tb> 20 <SEP> N-C <SEP> C-OCHs <SEP> little needles <SEP> N <SEP> 14, <SEP> 04 <SEP> N <SEP> 13, <SEP> 85
<tb> <SEP> I <SEP> I <SEP> I <SEP> I <SEP> F = 212, <SEP> 4-213, <SEP> 4 <SEP> (299, <SEP> 34)
<tb> <SEP> lithanol water
<tb> <SEP> 1 <SEP>:

   <SEP> 1)
<tb> <SEP> OCHs <SEP> 49, <SEP> 2 <SEP> light yellow, <SEP> ver-C <SEP> 60, <SEP> 18 <SEP> C <SEP> 60, <SEP> 23 < SEP> 351/12800
<tb> <SEP> felted <SEP> needles <SEP> H <SEP> 4, <SEP> 38 <SEP> H <SEP> 4, <SEP> 52 <SEP> 298/16000
<tb> <SEP> F = 181-182 <SEP> N <SEP> 14, <SEP> 04 <SEP> N <SEP> 13, <SEP> 79 <SEP> L-BGr
<tb> NN <SEP> I <SEP> (ltthanol-water <SEP> (299, <SEP> 34)
<tb> <SEP> N <SEP> N <SEP> 1 <SEP> 1 <SEP>:

   <SEP> 1)
<tb> <SEP> OCHs
<tb> <SEP> OCHs <SEP> 70, <SEP> 5 <SEP> light yellow, <SEP> ver-C <SEP> 58, <SEP> 34 <SEP> C <SEP> 58, <SEP> 27 < SEP> 330/19800
<tb> <SEP> S <SEP> S- <SEP>! <SEP> felted <SEP> needles <SEP> H <SEP> 4, <SEP> 59 <SEP> H <SEP> 4, <SEP> 70 <SEP> 258/9900
<tb> 22 <SEP> NC <SEP> G-OCHs <SEP> F = 167-168 <SEP> N <SEP> 12, <SEP> 76 <SEP> N <SEP> 12, <SEP> 65 <SEP > L-GGr
<tb> <SEP> ii <SEP> w <SEP> (ethanol-water <SEP> (329, <SEP> 39)
<tb> <SEP> s <SEP> 2 <SEP>:

   <SEP> 3)
<tb> <SEP> OC2H5 <SEP> 85, <SEP> 5 <SEP> Colorless, <SEP> fine, <SEP> C <SEP> 64, <SEP> 62 <SEP> C <SEP> 64, <SEP > 26 <SEP> 332/21900
<tb> <SEP> S <SEP> I <SEP> matted <SEP> H <SEP> 5, <SEP> 08 <SEP> H <SEP> 5, <SEP> 13 <SEP> 304/15600
<tb> 23 <SEP> NC <SEP> C-C'Hs <SEP> little needles <SEP> N <SEP> 14, <SEP> 13 <SEP> N <SEP> 14, <SEP> 25 <SEP> St -B
<tb> <SEP> ii <SEP> ii <SEP> F <SEP> = <SEP> 171-172 '<SEP> (297, <SEP> 39)
<tb> <SEP> (Athanal <SEP> (Athanol-water
<tb> <SEP> 4 <SEP>:

   <SEP> 3)
<tb> <SEP> S <SEP> 87, <SEP> 8 <SEP> Colorless, <SEP> glossy-C <SEP> 72, <SEP> 35 <SEP> C <SEP> 72, <SEP> 10 < SEP> 325/30000
<tb> 24 <SEP> zende, <SEP> small <SEP> H <SEP> 4, <SEP> 15 <SEP> H <SEP> 4, <SEP> 16 <SEP> L-B
<tb> <SEP> II <SEP> II <SEP> plate <SEP> N <SEP> 13, <SEP> 32 <SEP> N <SEP> 13, <SEP> 21
<tb> <SEP> N-N <SEP> F = 241, <SEP> 4-242, <SEP> 8 <SEP> (315, <SEP> 40)
<tb> <SEP> (dioxane-water
<tb> <SEP> 5 <SEP>:

   <SEP> 1)
<tb> <SEP> S,} <SEP> \ / 85, <SEP> 4 <SEP> Nearly colorless, <SEP> C <SEP> 70, <SEP> 56 <SEP> C <SEP> 70, <SEP> 68 <SEP> 322/20200
<tb>, <SEP>! <SEP>! <SEP> t <SEP> tvery <SEP> fine <SEP> H <SEP> 3, <SEP> 83 <SEP> H <SEP> 3, <SEP> 81 <SEP> 285/18700
<tb> <SEP> crystals <SEP> N <SEP> 14, <SEP> 52 <SEP> N <SEP> 14, <SEP> 32 <SEP> 275/18600
<tb> <SEP> N-N <SEP> F = 204, <SEP> 4-105, <SEP> 4 <SEP> (289, <SEP> 37) <SEP> M-HV
<tb> <SEP> (dioxane-ethanol
<tb> <SEP> water2 <SEP>: <SEP> 1 <SEP>:

   <SEP> 1)
<tb>
EMI6.1


<tb> No. <SEP> Formula <SEP> Off properties <SEP> Analysis <SEP> Amax
<tb> <SEP> loot <SEP> calculated <SEP> found
<tb> <SEP> in <SEP> ouzo <SEP> (Mol) <SEP> fluorescence
<tb> <SEP> S <SEP> 70, <SEP> 8 <SEP> Almost <SEP> colorless, <SEP> C <SEP> 59, <SEP> 98 <SEP> C <SEP> 60, <SEP> 16 <SEP> 292/20700
<tb> <SEP>,. <SEP> small <SEP> H <SEP> 3, <SEP> 36 <SEP> H <SEP> 3, <SEP> 41 <SEP> none
<tb> 26 <SEP> N / <SEP> C \ = t <SEP> plate <SEP> N <SEP> 23, <SEP> 32 <SEP> N <SEP> 23, <SEP> 28
<tb> <SEP> N-N <SEP> F = 236, <SEP> 5-238 <SEP> (240, <SEP> 29)
<tb> <SEP> (dioxane-ethanol
<tb> <SEP> water <SEP> 4 <SEP>: <SEP> 3 <SEP>:

   <SEP> 3)
<tb> <SEP> vSs <SEP> 81, <SEP> 4 <SEP> colorless, <SEP> glossy-C <SEP> 65, <SEP> 25 <SEP> C <SEP> 65, <SEP> 18 < SEP> 304/23000
<tb> 27 <SEP> <<SEP> C <SEP> C¯ <<SEP> zende <SEP> platelets <SEP> H <SEP> 3, <SEP> 79 <SEP> H <SEP> 3, <SEP > 65 <SEP> none
<tb> <SEP> F = 154, <SEP> 2-155 <SEP> N <SEP> 17, <SEP> 56 <SEP> N <SEP> 17, <SEP> 55
<tb> <SEP> N-N <SEP> (ethanol-water <SEP> (239, <SEP> 29)
<tb> <SEP> 2 <SEP>: <SEP> 1)
<tb> <SEP> CH3 <SEP> 83 <SEP> Colorless, <SEP> glossy-C <SEP> 66, <SEP> 38 <SEP> C <SEP> 66, <SEP> 36 <SEP> 307/23500
<tb> <SEP> zende, <SEP> small <SEP> H <SEP> 4, <SEP> 38 <SEP> H <SEP> 4, <SEP> 29 <SEP> M-WO
<tb> 28 <SEP> c <SEP> C¯ <<SEP> platelets <SEP> N <SEP> 16, <SEP> 59 <SEP> N <SEP> 16, <SEP> 73
<tb> <SEP> F <SEP> I <SEP> 119-120 <SEP> (253, <SEP> 31)
<tb> <SEP> N-N <SEP> (ethanol-water
<tb> <SEP> 1 <SEP>:

   <SEP> 2)
<tb> <SEP> 86, <SEP> 2 <SEP> colorless, <SEP> glossy-C <SEP> 66, <SEP> 38 <SEP> C <SEP> 66, <SEP> 24 <SEP> 310 / 24000
<tb> 29 <SEP> c <SEP> C <SEP> C - CHszende, <SEP> small <SEP> H <SEP> 4, <SEP> 38 <SEP> H <SEP> 4, <SEP> 48 <SEP> SB
<tb> <SEP> plate <SEP> N <SEP> 16, <SEP> 59 <SEP> N <SEP> 16, <SEP> 72
<tb> <SEP> NN <SEP> F = <SEP> 158, <SEP> 4-159, <SEP> 4 <SEP> (253, <SEP> 31)
<tb> <SEP> (ethanol-water
<tb> <SEP> 1 <SEP>: <SEP> 1)
<tb> <SEP> CH3 <SEP> 84, <SEP> 2 <SEP> Colorless, <SEP> glossy-C <SEP> 69, <SEP> 12 <SEP> C <SEP> 69, <SEP> 01 < SEP> 310/25300
<tb> <SEP> no <SEP> needles <SEP> H <SEP> 5, <SEP> 80 <SEP> H <SEP> 5, <SEP> 99 <SEP> SS-B
<tb> 30 <SEP> C <SEP> C-CH3 <SEP> F <SEP> = <SEP> 162-163, <SEP> 5 '<SEP> N <SEP> 14, <SEP> 23 <SEP> N <SEP> 14, <SEP> 46
<tb> <SEP> N = <SEP> N-N <SEP> (ethanol-water <SEP> (295, <SEP> 41)
<tb> <SEP> 3 <SEP>:

   <SEP> 1)
<tb> <SEP> CIL <SEP> 90, <SEP> 6 <SEP> Colorless, <SEP> glossy-C <SEP> 67, <SEP> 39 <SEP> C <SEP> 67, <SEP> 43 < SEP> 313/24500
<tb> <SEP> sa <SEP> zende, <SEP> matted <SEP> H <SEP> 4, <SEP> 90 <SEP> H <SEP> 4, <SEP> 79 <SEP> S-B
<tb> <SEP> c <SEP> CHs <SEP> Nddelchen <SEP> and <SEP> N <SEP> 15, <SEP> 72 <SEP> N <SEP> 15, <SEP> 82
<tb> N = / | 1 <SEP> 1l <SEP> \ = / plate <SEP> (267, <SEP> 34)
<tb> <SEP> N <SEP> N <SEP> F = <SEP> 144, <SEP> 4-145, <SEP> 2
<tb> <SEP> (ethanol)
<tb> <SEP> Cl <SEP> 91, <SEP> 5 <SEP> Colorless, <SEP> glossy-C <SEP> 57, <SEP> 04 <SEP> C <SEP> 57, <SEP> 24 < SEP> 303/21600
<tb> <SEP> end, <SEP> short <SEP> H <SEP> 2, <SEP> 95 <SEP> H <SEP> 3, <SEP> 04 <SEP> SS-B
<tb> 32 <SEP> r <SEP> r <SEP> \ little needle <SEP> N <SEP> 15, <SEP> 35 <SEP> N <SEP> 15, <SEP> 38
<tb> <SEP> F = <SEP> 147, <SEP> 6-148, <SEP> 2 <SEP> (273, <SEP> 75)

  
<tb> <SEP> N-N <SEP> (ethanol)
<tb> <SEP> S <SEP> 93, <SEP> 7 <SEP> Colorless, <SEP> very <SEP> C <SEP> 57, <SEP> 04 <SEP> C <SEP> 57, <SEP> 09 <SEP> 309/24600
<tb> 33 <SEP>. <SEP> C <SEP> C - fine, <SEP> shiny <SEP> H <SEP> 2, <SEP> 95 <SEP> H <SEP> 2, <SEP> 85 <SEP> SS-B
<tb> <SEP> needle <SEP> N <SEP> 15, <SEP> 35 <SEP> N <SEP> 15, <SEP> 26
<tb> <SEP> N-N <SEP> F = 187, <SEP> 6-188, <SEP> 4 <SEP> (273, <SEP> 75)
<tb> <SEP> (ethanol)
<tb> <SEP> C1 <SEP> 93, <SEP> 5 <SEP> Colorless, <SEP> very <SEP> C <SEP> 50, <SEP> 66 <SEP> C <SEP> 50, <SEP> 79 <SEP> 311/25800
<tb> <SEP> S <SEP> | <SEP> small <SEP> crystals <SEP> H <SEP> 2, <SEP> 29 <SEP> H <SEP> 2, <SEP> 04 <SEP> SS-B
<tb> 34 <SEP> C / c <SEP> C, <SEP> F = 209-209, <SEP> 8 '<SEP> N <SEP> 13, <SEP> 64 <SEP> N <SEP> 13 , <SEP> 52
<tb> <SEP> (Dioxane-Ethanol- <SEP> (308, <SEP> 20)

  
<tb> <SEP> N-N <SEP> water <SEP> 7 <SEP>: <SEP> 2 <SEP>: <SEP> 1)
<tb> <SEP> OCHs <SEP> 64 <SEP> Almost <SEP> colorless, <SEP> C <SEP> 62, <SEP> 43 <SEP> C <SEP> 62, <SEP> 50 <SEP> 325 / 20900
<tb> <SEP> small <SEP> crystals <SEP> H <SEP> 4, <SEP> 12 <SEP> H <SEP> 4, <SEP> 35 <SEP> 301/18000
<tb> 35 <SEP> F = 153, <SEP> 4-153, <SEP> 8 <SEP> N <SEP> 15, <SEP> 60 <SEP> N <SEP> 15, <SEP> 74 <SEP > M-WG
<tb> <SEP> (ethanol-water <SEP> (269, <SEP> 33)
<tb> <SEP> N-N <SEP> 1 <SEP>:

   <SEP> 4)
<tb>
EMI7.1


<tb> No. <SEP> Formula <SEP> Off properties <SEP> Analysis <SEP> / s
<tb> <SEP> loot <SEP> calculates <SEP> found
<tb> <SEP> in <SEP> ouzo <SEP> (Mol) <SEP> fluorescence
<tb> <SEP> OCHs <SEP> 79, <SEP> 5 <SEP> Colorless, <SEP> very <SEP> C <SEP> 62, <SEP> 43 <SEP> C <SEP> 62, <SEP> 73 <SEP> 305/21200
<tb> <SEP> Ss <SEP> | <SEP> small, <SEP> shiny <SEP> H <SEP> 4, <SEP> 12 <SEP> H <SEP> 4, <SEP> 25 <SEP> SS-B
<tb> == / ") <SEP> t) <SEP>! <SEP> \ = / F = <SEP> 101, <SEP> 4-103 <SEP> (269, <SEP> 33)
<tb> <SEP> II <SEP> II
<tb> <SEP> N-N <SEP> N <SEP> (ethanol-water
<tb> <SEP> 1 <SEP>:

   <SEP> 2)
<tb> <SEP> S. <SEP> 90, <SEP> 3 <SEP> Colorless, <SEP> glossy-C <SEP> 62, <SEP> 43 <SEP> C <SEP> 62, <SEP> 44 <SEP> 321/26700
<tb> 37 <SEP> S-CC- \ OCH3zende, <SEP> small <SEP> H <SEP> 4, <SEP> 12 <SEP> H <SEP> 4, <SEP> 06 <SEP> S-B
<tb> <SEP> Nqdelchen <SEP> N <SEP> 15, <SEP> 60 <SEP> N <SEP> 15, <SEP> 52
<tb> <SEP> F = 156-157 <SEP> (269, <SEP> 33)
<tb> <SEP> (anol-dioxane
<tb> <SEP> water <SEP> 2 <SEP>: <SEP> 1 <SEP>:

   <SEP> 2)
<tb> <SEP> OCH <<SEP> 77 Colorless, <SEP> glossy <SEP> C <SEP> 63, <SEP> 58 <SEP> C <SEP> 63, <SEP> 66 <SEP> 326/23100
<tb> <SEP> c) <SEP> zende <SEP> needles <SEP> H <SEP> 4, <SEP> 62 <SEP> H <SEP> 4, <SEP> 73 <SEP> 302/17900
<tb> 38 <SEP> ¯C <SEP> C¯ <¯CH8 <SEP> and <SEP> plates <SEP> N <SEP> 14, <SEP> 83 <SEP> N <SEP> 14, <SEP> 95 <SEP> M-MV
<tb> <SEP> F = 160-160, <SEP> 5 <SEP> (283, <SEP> (283,
<tb> <SEP> N-N <SEP> (ethanol-water
<tb> <SEP> 3 <SEP>: <SEP> 4)
<tb> <SEP> OCHs <SEP> 81, <SEP> 6 <SEP> Colorless, <SEP> matted <SEP> C <SEP> 63, <SEP> 58 <SEP> C <SEP> 63, <SEP> 54 <SEP> 332/18400
<tb> <SEP> N <SEP> needle <SEP> H <SEP> 4, <SEP> 62 <SEP> H <SEP> 4, <SEP> 55 <SEP> 302/17400
<tb> 39 <SEP> r'r <SEP> F = <SEP> 152, <SEP> 6-153, <SEP> 2 <SEP> N14, <SEP> 83 <SEP> N14, <SEP> 87 < SEP> MB
<tb> <SEP> IN-N <SEP> s <SEP> 3 <SEP>:

   <SEP> 4)
<tb> <SEP> CH3
<tb> <SEP> OCHs <SEP> 1 <SEP> Colorless, <SEP> ver-C <SEP> 55, <SEP> 35 <SEP> C <SEP> 55, <SEP> 21 <SEP> 332/18200
<tb> <SEP> flipped, <SEP> shining <SEP> H <SEP> 3, <SEP> 32 <SEP> H <SEP> 3, <SEP> 11 <SEP> 295/18000
<tb> 40 <SEP> C-Nlidelchen <SEP> N <SEP> 13, <SEP> 83 <SEP> N <SEP> 13, <SEP> 77 <SEP> S-V
<tb> <SEP> F = 199, <SEP> 4-199, <SEP> 8 <SEP> (303, <SEP> 78)
<tb> <SEP> N-N <SEP> (dioxane-ethanol
<tb> <SEP> water <SEP> 2 <SEP>: <SEP> 1 <SEP>:

   <SEP> 2)
<tb> <SEP> S <SEP> 90, <SEP> 8 <SEP> colorless, <SEP> ver-C <SEP> 59, <SEP> 98 <SEP> C <SEP> 60, <SEP> 27 < SEP> 311/23200
<tb> 41 <SEP> ¯C <SEP> C¯ <<SEP> felted <SEP> needles <SEP> H <SEP> 3, <SEP> 36 <SEP> H <SEP> 3, <SEP> 30 < SEP> SS-B
<tb> <SEP> F = 219-219, <SEP> 2 <SEP> N <SEP> 23, <SEP> 32 <SEP> N <SEP> 23, <SEP> 01
<tb> <SEP> N <SEP> N <SEP> (Dioxane-Ethanol- <SEP> (240, <SEP> 29)
<tb> <SEP> water <SEP> 1 <SEP>: <SEP> 1 <SEP>:

   <SEP> 1)
<tb> <SEP>, <SEP> S <SEP> 78, <SEP> 6 <SEP> Colorless, <SEP> fine, <SEP> C <SEP> 65, <SEP> 25 <SEP> C <SEP> 65, <SEP> 05 <SEP> 310/23900
<tb> 42 <SEP> <¯C <SEP> C¯ <SEP> matted <SEP> H <SEP> 3, <SEP> 79 <SEP> H <SEP> 3, <SEP> 97 <SEP> SS- B.
<tb> <SEP> / l <SEP> \ = / little needle <SEP> N <SEP> 17, <SEP> 56 <SEP> N <SEP> 17, <SEP> 82
<tb> <SEP> F = 139, <SEP> 2-141 <SEP> (239, <SEP> 59)
<tb> <SEP> (ethanol)
<tb> <SEP> CH3 <SEP> 83 <SEP> Almost <SEP> colorless, <SEP> C <SEP> 66, <SEP> 38 <SEP> C <SEP> 66, <SEP> 32 <SEP> 312 / 24600
<tb> <SEP> matted <SEP> needle H <SEP> 4, <SEP> 38 <SEP> H <SEP> 4, <SEP> 48 <SEP> none
<tb> 43 <SEP> <<SEP> C <SEP> C <SEP> <<SEP> chen <SEP> N <SEP> 16, <SEP> 59 <SEP> N <SEP> 16, <SEP> 82
<tb> <SEP> F = 119, <SEP> 5-120, <SEP> 2 <SEP> (253, <SEP> 31)
<tb> <SEP> N-N <SEP> (ithanol-water
<tb> <SEP> 3 <SEP>:

   <SEP> 2)
<tb> <SEP> S <SEP> 83, <SEP> 8 <SEP> Almost <SEP> colorless, <SEP> C <SEP> 66, <SEP> 38 <SEP> C <SEP> 66, <SEP> 46 <SEP> 315/26700
<tb> 44 <SEP> C '"- c <SEP> C''C-CH <SEP>! <SEP>! <SEP> short <SEP> needles <SEP> H <SEP> 4, <SEP> 38 <SEP> H <SEP> 4, <SEP> 08 <SEP> S-WB
<tb> <SEP> F = 144, <SEP> 6-146, <SEP> 8 <SEP> N <SEP> 16, <SEP> 59 <SEP> N <SEP> 16, <SEP> 70
<tb> <SEP> N-N <SEP> (ethanol) <SEP> (253, <SEP> 31)
<tb>
EMI8.1


<tb> <SEP> No.

   <SEP> Formula <SEP> Off properties <SEP> Analysis <SEP> Fluorescence
<tb> <SEP> loot <SEP> calculated <SEP> found
<tb> <SEP> in, <SEP> zozo <SEP> (Mol) <SEP> imtlx / E
<tb> <SEP> CH3 <SEP> 88, <SEP> 1 <SEP> Almost <SEP> colorless, <SEP> C <SEP> 69, <SEP> 12 <SEP> C <SEP> 68, <SEP> 93 <SEP> 315 <SEP>! <SEP> 26800
<tb> <SEP> fine <SEP> Nadelchn <SEP> H <SEP> 5, <SEP> 80 <SEP> H <SEP> 6, <SEP> 09 <SEP> none
<tb> 45 <SEP> t <SEP> -C <SEP> C- <SEP> -C-CHsF = 121-122 <SEP> N14, <SEP> 23 <SEP> N <SEP> 14, <SEP> 18th
<tb> <SEP> (ethanol-water <SEP> (295, <SEP> 41)
<tb> <SEP> N-N <SEP> 3 <SEP>:

   <SEP> 2)
<tb> <SEP> CH3 <SEP> 87 <SEP> colorless, <SEP> ver-C <SEP> 67, <SEP> 39 <SEP> C <SEP> 67, <SEP> 35 <SEP> 317/26200
<tb> <SEP> felted, <SEP> shiny <SEP> H <SEP> 4, <SEP> 90 <SEP> H <SEP> 4, <SEP> 85 <SEP> St-WB
<tb> 46 <SEP> c <SEP> CH, <SEP> little pins <SEP> N <SEP> 15, <SEP> 72 <SEP> N <SEP> 15, <SEP> 50
<tb> <SEP> F = 136, <SEP> 5-137, <SEP> 5 <SEP> (267, <SEP> 34)
<tb> <SEP> N-N <SEP> (ethanol-water
<tb> <SEP> 3 <SEP>:

   <SEP> 1)
<tb> <SEP> S <SEP> 91, <SEP> 5 <SEP> Colorless, <SEP> fine, <SEP> C <SEP> 57, <SEP> 04 <SEP> C <SEP> 57, <SEP > 03 <SEP> 314/28700
<tb> 47 <SEP> <<SEP> -C <SEP> C- <SEP> -Cl glossy <SEP> H <SEP> 2, <SEP> 95 <SEP> H <SEP> 2, <SEP> 86 < SEP> SB
<tb> <SEP> N-N <SEP> N <SEP> 15, <SEP> 35 <SEP> N <SEP> 15, <SEP> 24
<tb> <SEP> NN <SEP> F = <SEP> 197, <SEP> 5-198, <SEP> 8 <SEP> (273, <SEP> 75)
<tb> <SEP> (ethanol-dioxane
<tb> <SEP> 2 <SEP>: <SEP> 1)
<tb> <SEP> Cl <SEP> 88, <SEP> 2 <SEP> Colorless, <SEP> very <SEP> C <SEP> 50, <SEP> 66 <SEP> C <SEP> 50, <SEP> 38 <SEP> 314/27700
<tb> <SEP> fine <SEP> crystals <SEP> H <SEP> 2, <SEP> 29 <SEP> H <SEP> 2, <SEP> 24 <SEP> M-WB
<tb> 48 <SEP> c''cdF = 211, <SEP> 6-213, <SEP> 2 <SEP> N <SEP> 13, <SEP> 64 <SEP> N <SEP> 13, <SEP> 42
<tb> <SEP> N-N <SEP> 3 <SEP>: <SEP> 1 <SEP>: <SEP> 1)
<tb> NN <SEP> water <SEP> 3 <SEP>:

   <SEP> 1 <SEP>: <SEP> 1)
<tb> <SEP> 87, <SEP> 7 <SEP> Colorless, <SEP> very <SEP> C <SEP> 62, <SEP> 43 <SEP> C <SEP> 62, <SEP> 26 <SEP> 325/27400
<tb> 49 <SEP> C <SEP> 4 <SEP>: <SEP> -O'O \ N-OCH, <SEP> fine, <SEP> matted <SEP> H <SEP> 4, <SEP> 12 <SEP> H <SEP> 4, <SEP> 06 <SEP> LB
<tb> <SEP> little needles <SEP> N <SEP> 15, <SEP> 60 <SEP> N <SEP> 15, <SEP> 78
<tb> <SEP> F = 145-147 <SEP> (269, <SEP> 33)
<tb> <SEP> (ethanol)
<tb> <SEP> OCH3 <SEP> 87 <SEP> Colorless, <SEP> glossy-C <SEP> 63, <SEP> 58 <SEP> C <SEP> 63, <SEP> 69 <SEP> 333/25700
<tb> <SEP> no <SEP> needles <SEP> H <SEP> 4, <SEP> 62 <SEP> H <SEP> 4, <SEP> 70 <SEP> 305/17000
<tb> 50 <SEP> 14, <SEP> 83 <SEP> N <SEP> 14, <SEP> 74 <SEP> St-B
<tb> <SEP> (ethanol) <SEP> (283, <SEP> 34)
<tb> <SEP> N-N
<tb> <SEP> OCH3 <SEP> 71, <SEP> 2 <SEP> colorless, <SEP> fine, <SEP> C <SEP> 55, <SEP> 35 <SEP> C <SEP> 55,

   <SEP> 27 <SEP> 335/20600
<tb> <SEP> matted <SEP> H <SEP> 3, <SEP> 32 <SEP> H <SEP> 3, <SEP> 32 <SEP> 307/18800
<tb> 51 <SEP> N <SEP> 13, <SEP> 83 <SEP> N <SEP> 13, <SEP> 73 <SEP> M-B
<tb> <SEP> F = 211, <SEP> 3-211, <SEP> 8 <SEP> (303, <SEP> 78)
<tb> <SEP> NN <SEP> l <SEP> (Ethanol-Dioxane
<tb> <SEP> Cl <SEP> 4 <SEP>: <SEP> 1)
<tb> <SEP> S. <SEP> 69, <SEP> 1 <SEP> Colorless, <SEP> glossy-C <SEP> 59, <SEP> 98 <SEP> C <SEP> 59, <SEP> 78 <SEP> 303/24800
<tb> 52 <SEP> -C <SEP> C- <zende <SEP> platelets <SEP> H <SEP> 3, <SEP> 36 <SEP> H <SEP> 3, <SEP> 62 <SEP> none
<tb> <SEP> \ - NI <SEP>! <SEP>! <SEP>! <SEP>! <SEP> N == F = 201, <SEP> 3-202, <SEP> 7 <SEP> N23, <SEP> 32 <SEP> N <SEP> 23, <SEP> 25
<tb> <SEP> N-N <SEP> (Dioxan-Ethanol-S <SEP> 13, <SEP> 34 <SEP> S <SEP> 13, <SEP> 36
<tb> <SEP> water <SEP> 2 <SEP>: <SEP> 2 <SEP>:

   <SEP> 5) <SEP> (240, <SEP> 29)
<tb>
Example 2
10 parts of phosphorus pentasulfide are added to 8.03 parts of N-benzoyl-N'-isonicotinyl-hydramine in 75 parts by volume of N, N-dimethylaniline, with stirring, during which the reaction mixture warms up somewhat. The temperature is now brought to 60 to 65 in the course of 30 minutes, the mixture is stirred at 60 to 65 "for one hour, the temperature is then increased to 110 in the course of an hour and the reaction mixture is stirred for 12 hours at 110 to 115. Thereafter, it is brought to room temperature cooled, the reaction mixture mixed with 50 parts by volume of ethanol and 500 parts of water and finally made neutral with aqueous sodium hydroxide solution.

   The N, N-dimethylaniline is removed with steam and, after cooling to room temperature, the residue is suction filtered, washed with cold water and dried. About 6.8 parts are obtained, corresponding to 85.2 / o of theory, of 2 [pyridyl- (4 ')] -5-phenyl-1,3,4-thiadiazole of the formula (5) in the form of a slightly greenish powder, that melts at 172.8 to 181. Recrystallization three times from dioxane-water (1: 1) gives about 4.1 parts, corresponding to 51.4% of theory, pale yellow, shiny platelets with a melting point of 184.5 to 185.



   If 75 parts by volume of quinoline are used instead of the 75 parts by volume of N, N dimethylaniline, about 6.5 parts, corresponding to 81.5% of theory, are obtained 2- [pyridyl- (4 ')] -5-phenyl-1, 3, 4-thiadiazole, which after recrystallization from dioxane-water (1: 1) give about 3.0 parts, corresponding to 37.6 / o of theory, almost colorless, shiny flakes with a melting point of 176.5 to 182.4.



   Example 3
11.5 parts of N-furoyl-N'-benzoylhydrazine in 100 parts by volume of pyridine are mixed with 15 parts of phosphorus pentasulfide, the reaction mixture heating up. As soon as the exothermic reaction has subsided. the temperature is brought to 60 to 65 in the course of 30 minutes. The mixture is stirred for 1 hour at 60 to 65, the temperature is increased in the course of 1 hour to reflux and the yellow reaction solution is stirred at a low boiling point for 15 hours. It is then cooled to room temperature, 50 parts by volume of ethanol, then 2500 parts of ice water are added in several portions and the mixture is neutralized with an aqueous sodium hydroxide solution.

   The 2 [furyl- (2)] -5-phenyl-1,3,4-thiadiazole of the formula
EMI9.1
 is sucked, washed with cold water and dried. About 6.5 parts, corresponding to 57 ouzo of theory, of an almost colorless, crystalline powder which melts at 107 to 107.6 are obtained. After five recrystallization from ethanol-water (3: 2), colorless, shiny needles with a melting point of 108.2 to 109.2 are obtained, which fluoresce weakly blue under ultraviolet light.



  Analysis: C ,, HO NS (228, 28) calculated: C 63, 14 H 3, 54 N 12, 28 S 14, 05 found: C 63, 15 H 3, 43 N 12, 31 S 13, 75 UV- Absorption in dioxane: 321 mu (8 = 30700).



   The table below describes a further 1, 3, 4 thiadiazole compounds which can be prepared according to the above procedure. The information on the yield relates to the pipe product, and the abbreviations in the column on fluorescence are the same as in Example 1.
EMI9.2


<tb>



  No. <SEP> Formula <SEP> Off properties <SEP> Analysis <SEP> Fluorescence
<tb> <SEP> loot <SEP> calculated <SEP> found
<tb> <SEP> in '' / o <SEP> (mol) <SEP> max's
<tb> <SEP> HC-CH <SEP> S <SEP> 81 <SEP> Almost <SEP> colorless, <SEP> C <SEP> 64, <SEP> 44 <SEP> C <SEP> 64, <SEP > 54 <SEP> 324/27900
<tb> 11 <SEP> C <SEP> C <SEP> C <SEP> CH3 <SEP> very <SEP> {one, <SEP> glän-H <SEP> 4, <SEP> 16 <SEP> H < SEP> 4, <SEP> 09 <SEP> MB
<tb> <SEP> 54 <SEP> X / 11 <SEP> llt <SEP> zendeKristalle <SEP> N11, <SEP> 56 <SEP> N11, <SEP> 73
<tb> <SEP> O <SEP> N-N <SEP> F = 110, <SEP> 1-110, <SEP> 3 <SEP> (242, <SEP> 29)
<tb> <SEP> (ethanol-water
<tb> <SEP> 1 <SEP>:

   <SEP> 1)
<tb> <SEP> HC-CH <SEP> S <SEP> CHs <SEP> 40, <SEP> 1 <SEP> Almost <SEP> colorless, <SEP> C <SEP> 67, <SEP> 58 <SEP > C <SEP> 67, <SEP> 33 <SEP> 324/28300
<tb> 55 <SEP> HC <SEP> CC <SEP> b <SEP> c <SEP> CHs <SEP> shiny <SEP> needles <SEP> H <SEP> 5, <SEP> 67 <SEP> H < SEP> 5, <SEP> 68 <SEP> SB
<tb> <SEP> 55 <SEP> F = 78, <SEP> 8-79, <SEP> 6 <SEP> N <SEP> 9, <SEP> 85 <SEP> N <SEP> 9, <SEP> 84
<tb> <SEP> O <SEP> NN <SEP> CHs <SEP> (ethanol-water <SEP> (284, <SEP> 39)
<tb> <SEP> 5 <SEP>:

   <SEP> 3)
<tb> <SEP> HC-CH <SEP> S <SEP> 97, <SEP> 4 <SEP> Colorless, <SEP> glossy <SEP> C <SEP> 54, <SEP> 86 <SEP> C <SEP > 55, <SEP> 07 <SEP> 325/27800
<tb> 11 <SEP> 11 <SEP> zende <SEP> Ndlelchen <SEP> H <SEP> 2, <SEP> 69 <SEP> H <SEP> 2, <SEP> 79 <SEP> S-B
<tb> <SEP> \ / II <SEP> II <SEP> F = 143, <SEP> 8-144, <SEP> 6 <SEP> N <SEP> 10, <SEP> 66 <SEP> N <SEP > 10, <SEP> 62
<tb> <SEP> O <SEP> N-N <SEP> (ethanol-water <SEP> (262, <SEP> 73)
<tb> <SEP> 3 <SEP>:

   <SEP> 1)
<tb> <SEP> HC-CH <SEP> S <SEP> Cl <SEP> 89, <SEP> 9 <SEP> Colorless, <SEP> giän <SEP> C <SEP> 48, <SEP> 50 <SEP > C <SEP> 48, <SEP> 04 <SEP> 326/27500
<tb> 57 <SEP> 11 <SEP> end, <SEP> very <SEP> small <SEP> H <SEP> 2, <SEP> 04 <SEP> H <SEP> 2, <SEP> 06 <SEP> SS-B
<tb> <SEP> \ <SEP> t <SEP> BEÅattchen <SEP> N <SEP> 9, <SEP> 43 <SEP> N <SEP> 9, <SEP> 27
<tb> <SEP> 0 <SEP> N-N <SEP> F = 159, <SEP> 8-160, <SEP> 7 <SEP> (297, <SEP> 18)
<tb> <SEP> (ethanol-water
<tb> <SEP> 4 <SEP>:

   <SEP> 1)
<tb> <SEP> HC-CH <SEP> S <SEP> OCI-L <SEP> 54, <SEP> 3 <SEP> colorless, <SEP> very <SEP> C <SEP> 60, <SEP> 45 <SEP> C <SEP> 60, <SEP> 66 <SEP> 331/25300
<tb> <SEP> fine <SEP> needles <SEP> H <SEP> 3, <SEP> 90 <SEP> H <SEP> 3, <SEP> 99 <SEP> S-WB
<tb> \ / 11 <SEP> lltz <SEP> F = 147-148 <SEP> N10, <SEP> 85 <SEP> N <SEP> 11, <SEP> 11
<tb> <SEP> 0 <SEP> N-N <SEP> (ethanol-water <SEP> (258, <SEP> 31)
<tb> <SEP> 1 <SEP>:

   <SEP> 1)
<tb>
EMI10.1


<tb> No. <SEP> Formula <SEP> Off properties <SEP> Analysis <SEP> fluorescence
<tb> <SEP> loot <SEP> calculated <SEP> found ..
<tb> <SEP> in <SEP> O / o <SEP> (MOI)
<tb> <SEP> HC-CH <SEP> S <SEP> 93, <SEP> 7 <SEP> Almost <SEP> colorless, <SEP> C <SEP> 60, <SEP> 45 <SEP> C <SEP > 60, <SEP> 52 <SEP> 330/30800
<tb> 11 <SEP> 11 <SEP> matted eyelets <SEP> H <SEP> 3, <SEP> 90 <SEP> H <SEP> 4, <SEP> 05 <SEP> S-WB
<tb> <SEP> F = 102, <SEP> 1-103, <SEP> 1 <SEP> N <SEP> 10, <SEP> 85 <SEP> N <SEP> 11, <SEP> 05
<tb> <SEP> O <SEP> N-N <SEP> (ethanol-water <SEP> (258, <SEP> 31)
<tb> <SEP> 1 <SEP>:

   <SEP> 1)
<tb> <SEP> HC-CH <SEP> S <SEP> 84 <SEP> Colorless, <SEP> very <SEP> C <SEP> 71, <SEP> 03 <SEP> C <SEP> 71, <SEP > 20 <SEP> 334/37100
<tb> 60 <SEP> 11 <SEP> small, <SEP> graceful <SEP> H <SEP> 3, <SEP> 97 <SEP> H <SEP> 4, <SEP> 17 <SEP> St- B.
<tb> <SEP> \ <SEP> <<SEP> plate <SEP> N <SEP> 9, <SEP> 20 <SEP> N <SEP> 9, <SEP> 08
<tb> <SEP> 0-N-N <SEP> F = <SEP> 170, <SEP> 6-172 <SEP> (304, <SEP> 38)
<tb> <SEP> (dioxane-water
<tb> <SEP> 5 <SEP>: <SEP> 2)
<tb> HC-CH <SEP> S <SEP> 68, <SEP> 2 <SEP> pale yellow, <SEP> glossy-C <SEP> 69, <SEP> 04 <SEP> C <SEP> 69, <SEP > 15 <SEP> 333/29400
<tb> <SEP> no <SEP> leaves <SEP> H <SEP> 3, <SEP> 62 <SEP> H <SEP> 3, <SEP> 55 <SEP> 293/15800
<tb> <SEP> fiL <SEP>;

   <SEP> cc <SEP> c <SEP> F = 141, <SEP> 8-143, <SEP> 4 <SEP> N <SEP> 10, <SEP> 07 <SEP> N <SEP> 10, <SEP > 18 <SEP> SS-WB
<tb> <SEP> O <SEP> N-N <SEP> (dioxane-water <SEP> (278, <SEP> 34)
<tb> <SEP> 5 <SEP>: <SEP> 3)
<tb> <SEP> HC-CH <SEP> S <SEP> 66, <SEP> 9 <SEP> colorless, <SEP> very <SEP> C <SEP> 57, <SEP> 63 <SEP> C <SEP > 57, <SEP> 65 <SEP> 323/22800
<tb> 62 <SEP> HC'CC <SEP> CnN <SEP> fine, <SEP> matted <SEP> H <SEP> 3, <SEP> 08 <SEP> H <SEP> 3, <SEP> 05 < SEP> SB
<tb> <SEP> \ / 11 <SEP> 11 <SEP> \ S <SEP> Needle <SEP> N <SEP> 18, <SEP> 33 <SEP> N <SEP> 18, <SEP> 40
<tb> <SEP> 0 <SEP> N-N <SEP> F = <SEP> 175, <SEP> 4-176, <SEP> 6 <SEP> (229, <SEP> 27)
<tb> <SEP> (ethanol-water
<tb> <SEP> 2 <SEP>:

   <SEP> 1)
<tb> <SEP> HC-CH <SEP> S <SEP> HC-CH <SEP> 74, <SEP> 3 <SEP> pale yellow, <SEP> very <SEP> C <SEP> 55, <SEP> 04 <SEP> C <SEP> 54, <SEP> 89 <SEP> 332/24200
<tb> "" / \ "" fine, <SEP> matted <SEP> H <SEP> 2, <SEP> 77 <SEP> H <SEP> 2, <SEP> 56 <SEP> SS-B
<tb> <SEP> needle <SEP> N <SEP> 12, <SEP> 84 <SEP> N12, <SEP> 78
<tb> <SEP> O <SEP> N-N <SEP> 0 <SEP> F = 117, <SEP> 6-118, <SEP> 4 <SEP> (218, <SEP> 24)
<tb> <SEP> (ethanol-water
<tb> <SEP> 1 <SEP>:

   <SEP> 3)
<tb> <SEP> Cl <SEP> Cl <SEP> 84, <SEP> 9 <SEP> pale yellow, <SEP> glossy-C <SEP> 48, <SEP> 50 <SEP> C <SEP> 48, < SEP> 31 <SEP> 323/25800
<tb> <SEP> CC <SEP> S <SEP> numerous <SEP> leaves <SEP> H <SEP> 2, <SEP> 04 <SEP> H <SEP> 1, <SEP> 76 <SEP> none
<tb> <SEP> F = 165-165, <SEP> 6 <SEP> N <SEP> 9, <SEP> 43 <SEP> N <SEP> 9, <SEP> 41
<tb> <SEP> 64 <SEP> HC \ / Cu <SEP> CI <SEP> t <SEP> (dioxane-water <SEP> (297, <SEP> 18)
<tb> <SEP> 11 <SEP> 11 <SEP> 2 <SEP>:

   <SEP> 1)
<tb> <SEP> Cl <SEP> Cl <SEP> 69, <SEP> 5 <SEP> pale yellow, <SEP> very <SEP> C <SEP> 43, <SEP> 46 <SEP> C <SEP> 43 , <SEP> 58 <SEP> 326/28800
<tb> <SEP> fine, <SEP> matted <SEP> H <SEP> 1, <SEP> 52 <SEP> H <SEP> 1, <SEP> 35 <SEP> SS-GrB
<tb> <SEP> N <SEP> Needle <SEP> N <SEP> 8, <SEP> 45 <SEP> N <SEP> 8, <SEP> 59
<tb> 65 <SEP> HC <SEP> CC <SEP> C <SEP> C1 <SEP> F = 219-219, <SEP> 8 <SEP> (331, <SEP> 63)
<tb> <SEP> oui <SEP> N-N <SEP> (dioxane-water
<tb> <SEP> 6 <SEP>:

   <SEP> 1)
<tb> <SEP> C1 <SEP> Cl <SEP> 71, <SEP> 5 <SEP> light yellow, <SEP> very <SEP> C <SEP> 47, <SEP> 72 <SEP> C <SEP> 47 , <SEP> 84 <SEP> 334/29800
<tb> <SEP> CC <SEP> S <SEP> fine, <SEP> matted <SEP> H <SEP> 2, <SEP> 46 <SEP> H <SEP> 2, <SEP> 50 <SEP> SS -GrB
<tb> <SEP> N <SEP> needle <SEP> N <SEP> 8, <SEP> 56 <SEP> N <SEP> 8, <SEP> 70
<tb> 66 <SEP> HC <SEP> C-C <SEP> / <SEP> OCHs <SEP> F = 185, <SEP> 6-186 <SEP> (327, <SEP> 20)
<tb> <SEP> O <SEP> NN <SEP> (dioxane-water
<tb> <SEP> 3 <SEP>:

   <SEP> 1)
<tb> <SEP> Cl <SEP> Cl <SEP> 56, <SEP> 4 <SEP> Almost <SEP> colorless, <SEP> C <SEP> 44, <SEP> 31 <SEP> C <SEP> 43 , <SEP> 89 <SEP> 323/24400
<tb> <SEP> very <SEP> fine, <SEP> ver-H <SEP> 1, <SEP> 69 <SEP> H <SEP> 1, <SEP> 70 <SEP> S-B
<tb> <SEP> C-C <SEP> S <SEP> felted <SEP> needles <SEP> N <SEP> 14, <SEP> 09 <SEP> N13, <SEP> 99
<tb> 67 <SEP> HC <SEP> CC <SEP> C \ / F = <SEP> 162, <SEP> 6-164, <SEP> 6 <SEP> (298, <SEP> 16)
<tb> <SEP> O <SEP> N <SEP> (ethanol-water
<tb> <SEP> 5 <SEP>:

   <SEP> 2)
<tb>
EMI11.1


<tb> No. <SEP> Formula <SEP> Off properties <SEP> Analysis <SEP> fluorescence
<tb> <SEP> beube <SEP> deliberately <SEP> found
<tb> <SEP> in <SEP> / o <SEP> GMol) <SEP> imax / e
<tb> <SEP> d <SEP> Cl <SEP> 0. <SEP> Cl <SEP> 86, <SEP> 7 light yellow, <SEP> very <SEP> C <SEP> 33, <SEP> 74 <SEP> C <SEP> 34, <SEP> 03 <SEP> 348/29500
<tb> <SEP> CC <SEP> S <SEP> CC <SEP> fine, <SEP> matted <SEP> H <SEP> 0, <SEP> 56 <SEP> H <SEP> 0, <SEP> 59 <SEP> 337/29600
<tb> <SEP> II <SEP> II / \ <SEP> 11 <SEP> ll <SEP> little needles <SEP> N <SEP> 7, <SEP> 87 <SEP> N <SEP> 8, <SEP> 02 <SEP> L-BGr
<tb> 68 <SEP> HCC-C <SEP> C-CCHF-229, <SEP> 8-230, <SEP> 7 <SEP> (356, <SEP> 04)
<tb> <SEP> O <SEP> N-N <SEP> O <SEP> (dioxane-water
<tb> <SEP> 3 <SEP>:

   <SEP> 1)
<tb>
Example 4
7.1 part of thiophene-2-carboxylic acid hydrazide are stirred into 100 parts by volume of pyridine and cooled to below 5. Then 7.33 parts of p-methylbenzoyl chloride are added dropwise at 0 to 5, stirring is continued for 45 minutes at 0 to 5 and for a further 45 minutes at room temperature. The pale yellow reaction solution is heated to 80 to 85 in the course of one hour and stirred for a further 3 hours at this temperature. The solution is now cooled to room temperature and 15 parts of phosphorus pentasulfide are added, the reaction mixture heating up.

   As soon as the exothermic reaction has subsided, the temperature is brought to 60 and stirred at 60 to 65 for 1 hour. Finally, the temperature is increased to reflux over the course of 1 hour and the yellow reaction solution is stirred at a low boiling point for 12 hours. The mixture is cooled to room temperature, 50 parts by volume of ethanol and then 2500 parts of ice water are added in several portions and the mixture is neutralized with aqueous sodium hydroxide solution. The 2- [thienyl- (2 ')] - 5- [4 "-methyl-phenyl- (1")] - 1, 3, 4-thiadiazole of the formula
EMI11.2
 is sucked, washed with plenty of cold water and dried.

   The yellowish crude product is recrystallized from ethanol-water (2: 1) with the aid of activated charcoal. About 7.8 parts, corresponding to 60.5 / o of theory, of a pale yellow, crystalline powder which melts at 136 to 137.2 are obtained.



  Twice recrystallization from ethanol-water (2: 1) gives 6.5 parts, corresponding to 50.4 "/ o of theory, pale yellow, shiny platelets which melt at 137.2 to 138 and fluoresce light blue under ultraviolet light.



  Analysis: C13H10N2S2 (258, 36) calculated: C 60, 44 H 3, 90 N 10, 84 found: C 60, 57 H 3, 93 N 10, 91 UV absorption in dioxane:? @ Max = 329mÁ (? = 21100)? Max = 270mÁ (? = 5100)
The table below describes a further 1, 3, 4 thiadiazole compounds which can be prepared according to the above procedure. The information about the yield relate to the crude product which has been recrystallized once. The abbreviations in the column above fluorescence are the same as in Example 1.
EMI11.3


<tb>



  No. <SEP> Formula <SEP> Characteristic <SEP> Analysis <SEP> Xmas / e
<tb> <SEP> loot <SEP> calculated <SEP> found
<tb> <SEP> in <SEP> olo <SEP> (Mol) <SEP> fluorescence
<tb> <SEP> HC-CH <SEP> S <SEP> CH3 <SEP> 69, <SEP> 4 <SEP> colorless, <SEP> ver-C <SEP> 63, <SEP> 96 <SEP> C <SEP> 63, <SEP> 71 <SEP> 329/26600
<tb> 70 <SEP> 11 <SEP> 1 <SEP> felted <SEP> little nipple <SEP> H <SEP> 5, <SEP> 37 <SEP> H <SEP> 5, <SEP> 46 <SEP> 270 / 6400
<tb> <SEP> F = 109, <SEP> 4-110 <SEP> N <SEP> 9, <SEP> 32 <SEP> N <SEP> 9, <SEP> 20 <SEP> S-B
<tb> <SEP> S <SEP> N-N <SEP> CH3 <SEP> (ethanol-water <SEP> (300, <SEP> 45)
<tb> <SEP> 4 <SEP>:

   <SEP> 1)
<tb> <SEP> HC-CH <SEP> S <SEP> CHs <SEP> 54, <SEP> 3 <SEP> colorless, <SEP> glossy-C <SEP> 61, <SEP> 73 <SEP> C <SEP> 61, <SEP> 96 <SEP> 330/23000
<tb> <SEP> end <SEP> pliits. <SEP> H <SEP> 4, <SEP> 44 <SEP> H <SEP> 4, <SEP> 40 <SEP> 268/5800
<tb> 71 <SEP> H <SEP> j-C <SEP> C / -CHs <SEP> o
<tb> <SEP> \ <SEP> F = 170, <SEP> 4-171, <SEP> 2 <SEP> N <SEP> 10, <SEP> 29 <SEP> N <SEP> 10, <SEP> 14 <SEP> MB
<tb> <SEP> S <SEP> N-N <SEP> (ethanol-water <SEP> (272, <SEP> 40)
<tb> <SEP> 3 <SEP>:

   <SEP> 1)
<tb> <SEP> HC-CH <SEP> S <SEP> Cl <SEP> 70, <SEP> 6 <SEP> Farboles, <SEP> ver-C <SEP> 51, <SEP> 70 <SEP> C <SEP> 51, <SEP> 82 <SEP> 328/22900
<tb> <SEP> felted <SEP> needles <SEP> H <SEP> 2, <SEP> 53 <SEP> H <SEP> 2, <SEP> 39 <SEP> 267/6600
<tb> 72 <SEP> Hi <SEP> jC <SEP> C /, <SEP> 2-122, <SEP> 8 <SEP> N <SEP> 10, <SEP> 05 <SEP> N <SEP> 9 , <SEP> 80 <SEP> SB
<tb> <SEP> F = <SEP> 222,
<tb> <SEP> S <SEP> N-N <SEP> (ethanol) <SEP> (278, <SEP> 79)
<tb>
EMI12.1


<tb> No. <SEP> Formula <SEP> Off properties <SEP> Analysis <SEP> iSmas / e
<tb> <SEP> loot <SEP> calculated <SEP> found
<tb> <SEP> in <SEP> ío <SEP> (Mol) <SEP> fluorescence
<tb> <SEP> HC-CH <SEP> S <SEP> 67 <SEP> Colorless, <SEP> very <SEP> C <SEP> 51, <SEP> 70 <SEP> C <SEP> 51, <SEP > 61 <SEP> 330/26000
<tb> 3 <SEP> A "/ <SEP>.

   <SEP> fine needles <SEP> H <SEP> 2, <SEP> 53 <SEP> H <SEP> 2, <SEP> 34 <SEP> 272/7000
<tb> <SEP> F = 168, <SEP> 6-169, <SEP> 2 <SEP> N10, <SEP> 05 <SEP> N10, <SEP> 03 <SEP> S-B
<tb> <SEP> S <SEP> N-N <SEP> (dioxane-water <SEP> (278, <SEP> 79)
<tb> <SEP> 2 <SEP>: <SEP> 1)
<tb> <SEP> HC <SEP> CH <SEP> S <SEP> C1 <SEP> 58, <SEP> 8 <SEP> colorless, <SEP> very <SEP> C <SEP> 46, <SEP> 01 <SEP> C <SEP> 46, <SEP> 41 <SEP> 331/23300
<tb> 74 <SEP>! <SEP>!, / "-, - L <SEP> fine <SEP> needles <SEP> H <SEP> 1, <SEP> 93 <SEP> H <SEP> 1, <SEP> 88 <SEP> 270 / 6600
<tb> <SEP> \ / D <SEP> llo <SEP> F = 179, <SEP> 5-180 <SEP> N <SEP> 8, <SEP> 94 <SEP> N <SEP> 8, <SEP > 98 <SEP> S-HB
<tb> <SEP> S <SEP> N-N <SEP> (ethanol-water <SEP> (313, <SEP> 24)
<tb> <SEP> 9 <SEP>:

   <SEP> 1)
<tb> <SEP> HC-CH <SEP> S <SEP> 87, <SEP> 5 <SEP> pale yellow, <SEP> glossy-C <SEP> 56, <SEP> 91 <SEP> C <SEP> 56 , <SEP> 92 <SEP> 336/27200
<tb> 75 <SEP> HC <SEP> C-CC <SEP>. <SEP> OCH <SEP> zende <SEP> plates <SEP> H <SEP> 3, <SEP> 67 <SEP> H <SEP> 3, <SEP> 56 <SEP> 268/5300
<tb> <SEP> \ / ici <SEP> II <SEP> F = 166, <SEP> 4-167, <SEP> 6 <SEP> N <SEP> 10, <SEP> 21 <SEP> N <SEP > 10, <SEP> 40 <SEP> M-GrB
<tb> <SEP> S <SEP> N-N <SEP> (ethanol) <SEP> (274, <SEP> 37)
<tb> <SEP> HC-CH <SEP> S <SEP> OCHs <SEP> 30, <SEP> 5 <SEP> Almost <SEP> colorless, <SEP> C <SEP> 58, <SEP> 31 <SEP > C <SEP> 58, <SEP> 54 <SEP> 335/23800
<tb> 76 <SEP>! <SEP> i ./ \ <SEP> L <SEP> shiny <SEP> H <SEP> 4, <SEP> 19 <SEP> H <SEP> 4, <SEP> 04 <SEP> 268/5300
<tb> <SEP> Needle <SEP> N <SEP> 9, <SEP> 71 <SEP> N <SEP> 9, <SEP> 70 <SEP> S-WB
<tb> <SEP> S <SEP> N-N <SEP> F = <SEP> 191-191,

   <SEP> 6 <SEP> (288, <SEP> 40)
<tb> <SEP> (ethanol-water
<tb> <SEP> 2 <SEP>: <SEP> 1)
<tb> <SEP> HC-CH <SEP> S <SEP> OCHs <SEP> 54, <SEP> 8 <SEP> Nearly colorless, <SEP> C <SEP> 58, <SEP> 31 <SEP> C <SEP > 58, <SEP> 15 <SEP> 340121000
<tb> 77 <SEP> HC <SEP> C-CC <SEP> "<SEP> very <SEP> fine, <SEP> ver-H <SEP> 4, <SEP> 19 <SEP> H <SEP> 3 , <SEP> 99 <SEP> 267/5500
<tb> <SEP> felted <SEP> needles <SEP> N <SEP> 9, <SEP> 71 <SEP> N <SEP> 9, <SEP> 70 <SEP> S-WV
<tb> <SEP> S <SEP> N-N <SEP> F = 132, <SEP> 2-132, <SEP> 8 <SEP> (288, <SEP> 40)
<tb> <SEP> (ethanol-water
<tb> <SEP> 1 <SEP>:

   <SEP> 1)
<tb> <SEP> HC-CH <SEP> S <SEP> 74, <SEP> 9 <SEP> colorless, <SEP> glossy-C <SEP> 67, <SEP> 47 <SEP> C <SEP> 67 , <SEP> 55 <SEP> 339 <SEP>! <SEP> 36000
<tb> 78 <SEP> 11 <SEP> end, <SEP> very <SEP> kleme <SEP> H <SEP> 3, <SEP> 78 <SEP> H <SEP> 3, <SEP> 95 <SEP> St-B
<tb> <SEP> needle <SEP> N <SEP> 8, <SEP> 74 <SEP> N <SEP> 8, <SEP> 69
<tb> <SEP> S <SEP> N-N <SEP> F = 212-212, <SEP> 6 <SEP> (320, <SEP> 41)
<tb> <SEP> (dioxane-ethanol
<tb> <SEP> 5 <SEP>:

   <SEP> 1)
<tb> HC-CH <SEP> S <SEP> 84, <SEP> 9 <SEP> Almost <SEP> colorless, <SEP> C <SEP> 65. <SEP> 28 <SEP> C <SEP> 65, <SEP> 18 <SEP> 338/29600
<tb> <SEP> very <SEP> fine <SEP> H <SEP> 3, <SEP> 42 <SEP> H <SEP> 3, <SEP> 29 <SEP> 295/13300
<tb> <SEP> X / 11 <SEP> ll \ / little needle <SEP> N <SEP> 9, <SEP> 52 <SEP> N <SEP> 9, <SEP> 39 <SEP> 262/14800
<tb> <SEP> S <SEP> N-N <SEP> F = 165-167 <SEP> (294, <SEP> 38) <SEP> St-WB
<tb> <SEP> (ethanol-water
<tb> <SEP> 4 <SEP>:

   <SEP> 1)
<tb> <SEP> HC-CH <SEP> S <SEP> 64, <SEP> 3 <SEP> Colorless, <SEP> very <SEP> C <SEP> 53, <SEP> 85 <SEP> C <SEP > 54, <SEP> 10 <SEP> 327/22100
<tb> <SEP> 80 <SEP> HI <SEP> C - / \ <SEP> fine, <SEP> matted <SEP> H <SEP> 2, <SEP> 88 <SEP> H <SEP> 3, < SEP> 02 <SEP> 267/6300
<tb> <SEP> \ / 11 <SEP> 11 <SEP> \ = N <SEP> little needles <SEP> N17, <SEP> 13 <SEP> N17, <SEP> 26 <SEP> M-HGrB
<tb> S <SEP> N-N <SEP> F = 168-169 <SEP> (245, <SEP> 33)
<tb> <SEP> (dioxane-ethanol
<tb> <SEP> water <SEP> 2 <SEP>: <SEP> 2 <SEP>:

   <SEP> 3)
<tb> <SEP> HC-CH <SEP> S <SEP> HC-CH <SEP> 64, <SEP> 4 <SEP> light yellow, <SEP> fine, <SEP> C <SEP> 47, <SEP> 97 <SEP> C <SEP> 47, <SEP> 92 <SEP> 342/23500
<tb> 81 <SEP> HC <SEP> CC <SEP> 11 <SEP> graceful <SEP> H <SEP> 2, <SEP> 42 <SEP> H <SEP> 2, <SEP> 78 <SEP> 267 / 6000
<tb> <SEP> \ / D <SEP> II <SEP> \ / little needle <SEP> N <SEP> 11, <SEP> 19 <SEP> N <SEP> 11, <SEP> 30 <SEP> S- BGr
<tb> <SEP> S <SEP> NN <SEP> S <SEP> F = 157, <SEP> 2-157, <SEP> 8 <SEP> S <SEP> 38, <SEP> 42 <SEP> S <SEP> 38, <SEP> 34
<tb> <SEP> (ethanol) <SEP> (250, <SEP> 37)
<tb> <SEP> CH3 <SEP> 90, <SEP> 8 <SEP> pale yellow, <SEP> very <SEP> C <SEP> 62, <SEP> 90 <SEP> C <SEP> 62, <SEP> 73 <SEP> 337/26000
<tb> <SEP> 1 <SEP> fine, <SEP> matted <SEP> H <SEP> 4, <SEP> 93 <SEP> H <SEP> 4, <SEP> 86 <SEP> 273/6700
<tb> <SEP> needle <SEP> N <SEP> 9, <SEP> 78 <SEP> N <SEP> 10,

   <SEP> 06 <SEP> S-BGr
<tb> 82 <SEP> HsC-C <SEP> C-C <SEP> CCH3 <SEP> F = 165-166 <SEP> (286, <SEP> 41)
<tb> <SEP> (ethanol-water
<tb> <SEP> \ S <SEP> N-N
<tb>
EMI13.1


<tb> No. <SEP> Founel <SEP> Out-of-property <SEP> Analysis <SEP> imax / e
<tb> <SEP> loot <SEP> calculated <SEP> found
<tb> <SEP> in <SEP> solo <SEP> (Mol) <SEP> fluorescence
<tb> <SEP> CHs86 <SEP> Almost <SEP> colorless, <SEP> C <SEP> 65, <SEP> 81 <SEP> C <SEP> 65, <SEP> 75 <SEP> 338/25900
<tb> <SEP> 1 <SEP> fine <SEP> crystalline <SEP> H <SEP> 6, <SEP> 14 <SEP> H <SEP> 6, <SEP> 10 <SEP> 273/6700
<tb> <SEP> powder <SEP> N <SEP> 8, <SEP> 53 <SEP> N <SEP> 8, <SEP> 60 <SEP> St-GrB
<tb> 83 <SEP> HsC-C <SEP> CC <SEP> G / \ <SEP> C-GHs <SEP> F = 187, <SEP> 8-188, <SEP> 2 <SEP> (328, <SEP> 51)
<tb> <SEP> (ithanol water
<tb> <SEP> 2 <SEP>:

   <SEP> l)
<tb> <SEP> CHs <SEP> 70, <SEP> 7 <SEP> Colorless, <SEP> very <SEP> C <SEP> 63, <SEP> 96 <SEP> C <SEP> 64, <SEP> 11 <SEP> 338/27400
<tb> <SEP> HC-C <SEP> S <SEP> CHs <SEP> fine, <SEP> matted <SEP> H <SEP> 5, <SEP> 37 <SEP> H <SEP> 5, <SEP > 43 <SEP> 274/6700
<tb> <SEP> Needle <SEP> N <SEP> 9, <SEP> 32 <SEP> N <SEP> 9, <SEP> 50 <SEP> M-B
<tb> 84 <SEP> HsC-C <SEP> C-C <SEP> CCH3F = <SEP> 146, <SEP> 6-147, <SEP> 4 <SEP> (300, <SEP> 45)
<tb> <SEP> S <SEP> A <SEP> (ethanol-water
<tb> <SEP> "" "'" 5 <SEP>:

   <SEP> 2)
<tb> <SEP> CHs <SEP> 71, <SEP> 8 <SEP> Nearly close lots, <SEP> C <SEP> 54, <SEP> 80 <SEP> C <SEP> 54, <SEP> 73 <SEP> 341/25900
<tb> <SEP> HC-C <SEP> very <SEP> fine, <SEP> ver-H <SEP> 3, <SEP> 61 <SEP> H <SEP> 3, <SEP> 37 <SEP> 271 / 7300
<tb> <SEP> felted <SEP> needles <SEP> N <SEP> 9, <SEP> 13 <SEP> N <SEP> 9, <SEP> 23 <SEP> St-GrB
<tb> 85 <SEP> HsC-C <SEP> CI <SEP> C <SEP> t¯Cl <SEP> F = 168-169 <SEP> (306, <SEP> 85)
<tb> <SEP> (dioxane-water
<tb> <SEP> \ S / N-N
<tb> <SEP> CHs72, <SEP> 2 <SEP> light yellow, <SEP> glan-C <SEP> 49, <SEP> 27 <SEP> C <SEP> 49, <SEP> 40 <SEP> 345 / 26500
<tb> <SEP> HC-C <SEP> S <SEP> C1 <SEP> zendeNadelchen <SEP> H <SEP> 2, <SEP> 95 <SEP> H <SEP> 2, <SEP> 94 <SEP> 270/7700
<tb> <SEP> F = 170, <SEP> 8-171, <SEP> 4 <SEP> N <SEP> 8, <SEP> 21 <SEP> N <SEP> 8, <SEP> 18 <SEP> S-BGr
<tb> 86 <SEP> HaC \ / | <SEP> tC1 <SEP> (Ethanol-Dioxane <SEP> (341,

   <SEP> 30)
<tb> <SEP> S <SEP> N-N <SEP> water <SEP> 9 <SEP>: <SEP> 3 <SEP>: <SEP> 1)
<tb> <SEP> CHs <SEP> 86, <SEP> 1 <SEP> colorless, <SEP> glan-C <SEP> 59, <SEP> 57 <SEP> C <SEP> 59, <SEP> 73 < SEP> 341/29700
<tb> <SEP> HC-C <SEP> S <SEP> zendeNadeln <SEP> H <SEP> 4, <SEP> 67 <SEP> H <SEP> 4, <SEP> 71 <SEP> 278/7100
<tb> <SEP> F = 170, <SEP> 8-171, <SEP> 6 <SEP> N <SEP> 9, <SEP> 26 <SEP> N <SEP> 9, <SEP> 28 <SEP> SB
<tb> 87 <SEP> HsCCj / Cll <SEP> CItO <SEP> (Hs <SEP> (DioxanAthanol- <SEP> (302, <SEP> 43)
<tb> <SEP> S <SEP> NN <SEP> water <SEP> 1 <SEP>: <SEP> 1 <SEP>:

   <SEP> 1)
<tb> <SEP> CHs <SEP> 20 <SEP> weak <SEP> beige-C <SEP> 60, <SEP> 73 <SEP> C <SEP> 60, <SEP> 94 <SEP> 348/27100
<tb> <SEP> HC-C <SEP> <t <SEP> (TTHbraune, <SEP> glan-H <SEP> 5, <SEP> 10 <SEP> H <SEP> 5, <SEP> 05 <SEP > 270/6200
<tb> <SEP> II <SEP> II / \ <SEP> zende, <SEP> matted <SEP> N <SEP> 8, <SEP> 85 <SEP> N <SEP> 8, <SEP> 63 <SEP > SS-G
<tb> <SEP> 88 <SEP> H3C \ / | <SEP> <<SEP> needle <SEP> (316, <SEP> 45)
<tb> <SEP> S <SEP> N-N <SEP> \ t <SEP> F = <SEP> 139, <SEP> 2-139, <SEP> 6
<tb> <SEP> CHs <SEP> (methanol-water
<tb> <SEP> 1 <SEP>:

   <SEP> 1)
<tb> <SEP> CHs <SEP> 66, <SEP> 8 <SEP> pale yellow, <SEP> very <SEP> C <SEP> 57, <SEP> 81 <SEP> C <SEP> 57, <SEP> 82 <SEP> 347/29400
<tb> <SEP> 1 <SEP> S <SEP> OCHs <SEP> fine, <SEP> matted <SEP> H <SEP> 4, <SEP> 85 <SEP> H <SEP> 4, <SEP> 67 <SEP> 275/6400
<tb> <SEP> Needles <SEP> N <SEP> 8, <SEP> 43 <SEP> N <SEP> 8, <SEP> 45 <SEP> L-GrB
<tb> 89 <SEP> HsC- <SEP> C-i <SEP> II <SEP> OCHs <SEP> F = 182-182, <SEP> 5 <SEP> (332, <SEP> 45)
<tb> <SEP> S <SEP> N-N <SEP> (dioxane-water
<tb> <SEP> s <SEP> N-N <SEP> 1 <SEP>:

   <SEP> 1)
<tb> <SEP> CHs <SEP> 87, <SEP> 6 <SEP> pale yellow, <SEP> fine-C <SEP> 54, <SEP> 94 <SEP> C <SEP> 55, <SEP> 13 < SEP> 345/26500
<tb> <SEP> 1 <SEP> crystalline <SEP> H <SEP> 3, <SEP> 84 <SEP> H <SEP> 3, <SEP> 95 <SEP> 278/5700
<tb> <SEP> II <SEP> 11 / \ <SEP> powder <SEP> N <SEP> 10, <SEP> 68 <SEP> N <SEP> 10, <SEP> 67 <SEP> S-GrB
<tb> 90 <SEP> Hic-C <SEP>; -L <SEP> CC <SEP> CH <SEP> F = 142, <SEP> 8-144, <SEP> 2 <SEP> S <SEP> 24 , <SEP> 44 <SEP> S <SEP> 24, <SEP> 60
<tb> <SEP> S <SEP> \ / <SEP> (methanol-water <SEP> (262, <SEP> 36)
<tb> <SEP> 2 <SEP>:

   <SEP> 1)
<tb>
Example 5 10.2 parts of the diacylhydrazine of the formula
EMI13.2
 (which can be prepared by reacting 1 mole of 3,4-dimethoxybenzoyl chloride with 1 mole of thiophene-2-carboxylic acid hydrazide in pyridine), 15 parts of phosphorus pentasulfide are added to 100 parts by volume of 4-picoline, and the reaction mixture warms up. As soon as no further increase in temperature can be observed, the temperature is brought to 60 to 65 in the course of 15 minutes.

   The mixture is stirred for one hour at 60 to 65, the temperature is increased over the course of an hour to boiling and the yellow reaction solution is stirred for 12 hours under gentle reflux, the reaction product gradually crystallizing out. The mixture is cooled to room temperature, 50 parts by volume of ethanol and then 2500 parts of ice water are added in several portions and finally made neutral with aqueous sodium hydroxide solution. After suction filtering, washing with cold water and drying, about 8.05 parts, corresponding to 79.4! o the theory, 2 [thienyl- (2] -5- [3 ", 4" -dimethoxyphenyl- (1 ")] - 1,3,4thiadiazole of the formula
EMI14.1
 obtained in the form of pale yellow, fine crystals melting at 155.6 to 156.8.

   After three recrystallization from ethanol-water (3: 4), very fine, pale yellow needles with a melting point of 158.8 to 159.1¯ are obtained, which fluoresce weakly blue under ultraviolet light.



  Analysis: C14Ht202N2S2 (304, 40) calculated: C 55, 24 H 3, 97 N9, 20 found: C 55, 29 H 3, 88 N9, 12 UV absorption in dioxane:? Max = 342mÁ (? = 26800).



   If, instead of the 10 parts of phosphorus pentasulphide, 15 parts of phosphorus trisulphide are used, about 7.0 parts, corresponding to 69.1% of theory, 2- [thienyl- (2 ')] - 5- [3 ", 4" - dimethoxyphenyl- (1 ")] 1, 3, 4-thiadiazole, which is present in the form of a pale yellow, crystalline powder after four recrystallization from ethanol-water (1: 1), which melts at 158.5 to 158.9 .



   The same thiadiazole derivative is obtained if 15 parts of phosphorus sesquisulfide or phosphorus heptasulfide are used instead of 15 parts of phosphorus trisulfide.



   The table below describes a further 1, 3, 4 thiadiazole compounds which can be prepared using phosphorus pentasulfide according to the above procedure. The information on the yield relates to the crude product, and the abbreviations in the column on fluorescence are the same as in Example 1.
EMI14.2


<tb>



  No. <SEP> Formula <SEP> Off properties <SEP> Analysis), <SEP> max
<tb> <SEP> loot <SEP> calculated <SEP> found <SEP> max
<tb> <SEP> in "/ 0 <SEP> (Mol) <SEP> fluorescence
<tb> <SEP> HC-CH <SEP> S <SEP> 90, <SEP> 4 <SEP> Colorless, <SEP> very <SEP> C <SEP> 58, <SEP> 99 <SEP> C <SEP > 59, <SEP> 06 <SEP> 326/23300
<tb> 93 <SEP> HC <SEP> CC <SEP> C <SEP> n <SEP> fine needles <SEP> H <SEP> 3, <SEP> 30 <SEP> H <SEP> 3, <SEP> 31 <SEP> 268/7200
<tb> <SEP> \ / II <SEP> llw <SEP> F = 134, <SEP> 9-135, <SEP> 4 <SEP> N11, <SEP> 47 <SEP> N11, <SEP> 22 < SEP> MB
<tb> <SEP> (ethanol-water <SEP> (244, <SEP> 32)
<tb> <SEP> 1 <SEP>:

   <SEP> 1)
<tb> <SEP> HC-C <SEP> S <SEP> 98 <SEP> light yellow, <SEP> glossy-C <SEP> 57, <SEP> 11 <SEP> C <SEP> 57, <SEP> 18 <SEP> 348/25200
<tb> <SEP> 11 <SEP> 11 <SEP> zende <SEP> Nddelchen <SEP> H <SEP> 4, <SEP> 06 <SEP> H <SEP> 4, <SEP> 00 <SEP> 268 / 6400
<tb> 94 <SEP> 11 <SEP> N = / F = 163, <SEP> 2-165, <SEP> 2 <SEP> N15, <SEP> 37 <SEP> N15, <SEP> 07 <SEP> M-BGr
<tb> <SEP> (ethanol-water <SEP> (273, <SEP> 39)
<tb> <SEP> 2 <SEP>:

   <SEP> 1)
<tb> <SEP> HC-C <SEP> S <SEP> 86 <SEP> pale yellow, <SEP> very <SEP> C <SEP> 57, <SEP> 11 <SEP> C <SEP> 56, <SEP > 81 <SEP> 340/23100
<tb> CC <SEP> 11 / \ // - N \ <SEP> fine, <SEP> matted <SEP> H <SEP> 4, <SEP> 06 <SEP> H <SEP> 4, <SEP> 61 <SEP> 273/6800
<tb> <SEP> needle, <SEP> N <SEP> 15, <SEP> 37 <SEP> N15, <SEP> 35 <SEP> M-BGr
<tb> <SEP> S <SEP> NN <SEP> F = 133, <SEP> 2-135 <SEP> (273, <SEP> 39)
<tb> <SEP> (ethanol-water
<tb> <SEP> 1 <SEP>:

   <SEP> 2)
<tb>
Example 6
13.07 parts of the bis-diacylhydrazine of the formula (96)
EMI14.3
 (which can be prepared by reacting 2 moles of benzoyl chloride with 1 mole of furan-2, 5-dicarboxylic acid dihydrazide in pyridine) turn in 150 parts by volume of pyridine with stirring with 20 parts of phosphorus pentasulfide, the reaction mixture being heated. As soon as no further rise in temperature can be observed, the reaction mixture is brought to the boil over the course of 2t / 2 hours. The now clear solution is stirred at a low boiling point for 20 hours, the reaction product gradually crystallizing out.

   The mixture is cooled to room temperature, 50 parts by volume of ethanol and then 2000 parts of water are added in several portions and finally neutralized with an aqueous sodium hydroxide solution. After suction filtering, washing with cold and hot water and drying, about 12.9 parts, corresponding to 1000 / o of theory, 2- [5'-phenyl- (l "') - l', 3-thiadiazolyl- (20] - 5- [5 "phenyl-1" ") - 1", 3 ", 4" -thiadiazolyl- (2 ")] - furan of the formula
EMI15.1
 obtained in the form of a yellow powder melting at 258 to 265¯.

   After three recrystallizations from o-dichlorobenzene, 8.4 parts, corresponding to 64.9 / o of theory, are obtained, yellow, very fine, matted needles which melt at 264 to 265 and fluoresce strongly yellow under ultraviolet light.



  Analysis: C20H12ON4S2 (188, 48) calculated: C 61, 84 H 3, 11 N14, 42 found: C 61, 73 H 3, 12 N 14, 20 UV absorption in dioxane:? Max = 374mÁ (? = 38400) imaX = 365 m, u (± = 38600)? max = 299mÁ (? = 17200)
The table below describes a further 1, 3, 4 thiadiazole compounds which can be prepared according to the above procedure. The information on the yield relates to the crude product. The e-values marked with an * are uncertain because of the solubility of the connection.



  The abbreviations in the column about fluorescence have the same meaning as in example 1.
EMI15.2


<tb>



  No. <SEP> Formula <SEP> Off-Property <SEP>: <SEP> Eten <SEP> Analysis <SEP> A <SEP> a / e
<tb> <SEP> loot <SEP> calculated <SEP> found
<tb> <SEP> in <SEP> ouzo <SEP> (Mol) <SEP> fluorescence
<tb> <SEP> HsC <SEP> S <SEP> HC-CH <SEP> S <SEP> CHs <SEP> 100 light yellow, <SEP> C <SEP> 63, <SEP> 44 <SEP> C <SEP> 63, <SEP> 22 <SEP> 375/37000 <SEP>?
<tb> <SEP> lcristallines <SEP> powder <SEP> H <SEP> 3, <SEP> 87 <SEP> H <SEP> 3, <SEP> 87 <SEP> 366/37000 <SEP> X
<tb> <SEP> F <SEP> F = 215-218 <SEP> N <SEP> 13, <SEP> 45 <SEP> N <SEP> 13, <SEP> 35 <SEP> 302/17400
<tb> <SEP> N-N <SEP> O <SEP> N-N <SEP> (chlorobenzene) <SEP> (416, <SEP> 53) <SEP> St-GrG
<tb> <SEP> 100 <SEP> light yellow, <SEP> C <SEP> 63, <SEP> 44 <SEP> C <SEP> 63, <SEP> 16 <SEP> 378/37600
<tb> <SEP> S <SEP> HC-CH <SEP> S <SEP> crystalline <SEP> powder <SEP> H <SEP> 3, <SEP> 87 <SEP> H <SEP> 4,

   <SEP> 24 <SEP> 367/38000 <SEP>
<tb> <SEP> 99 <SEP> H <SEP> C <SEP> C <SEP> CC <SEP> <<SEP> F = 288-291 <SEP> N <SEP> 13, <SEP> 45 <SEP > N <SEP> 13, <SEP> 42 <SEP> 305/19400
<tb> <SEP> 99 <SEP> HsC <SEP> C <SEP> CC <SEP> CC <SEP> C-CH3 <SEP> (o-dichlorobenzene) <SEP> (416, <SEP> 53) <SEP > LG
<tb> <SEP> 100 <SEP> light yellow, <SEP> C <SEP> 67, <SEP> 17 <SEP> C <SEP> 67, <SEP> 15 <SEP> 378/42000
<tb> 100 <SEP> HsC <SEP> S <SEP> HC-CH <SEP> S <SEP> Cmcrystalline <SEP> powder <SEP> H <SEP> 5, <SEP> 64 <SEP> H <SEP> 5, <SEP> 75 <SEP> 368/42100 <SEP> X
<tb> <SEP> / \ <SEP> 11 <SEP> t / \ <SEP> I <SEP> F = via <SEP> 300 <SEP> N <SEP> 11, <SEP> 19 <SEP> N < SEP> 11, <SEP> 15 <SEP> 305/23000
<tb> <SEP> HsC-CI <SEP> d <SEP> N-N-CGHS <SEP> (Dioxane-Water <SEP> (500, <SEP> 70) <SEP> L-GGr
<tb> <SEP> 98, <SEP> 6 Lit <SEP> bright-C <SEP> 64, <SEP> 84 <SEP> C <SEP> 64,

   <SEP> 78 <SEP> 379/34000
<tb> <SEP> HsC <SEP> S <SEP> HC-CH <SEP> S <SEP> CH3 <SEP> yellow, <SEP> kri-H <SEP> 4, <SEP> 53 <SEP> H < SEP> 4, <SEP> 67 <SEP> 368/34000 <SEP> S
<tb> <SEP> / \ <SEP> II <SEP> II / sallin. <SEP> es <SEP> powder <SEP> N <SEP> 12, <SEP> 60 <SEP> N12, <SEP> 68 <SEP> 310/18000
<tb> 101 <SEP> H3C <SEP> C <SEP> CC <SEP> CC-cFb <SEP> F = 280, <SEP> 4-281- <SEP> (444, <SEP> 59) <SEP> LG
<tb> <SEP> N-N <SEP> 0 <SEP> N-N <SEP> (chlorobenzene)
<tb> <SEP> N-N <SEP> O <SEP> N-N
<tb> <SEP> 100 <SEP> light yellow, <SEP> fine-C <SEP> 52, <SEP> 52 <SEP> C <SEP> 52, <SEP> 54 <SEP> 376/38000
<tb> <SEP> ci <SEP> S <SEP> HC-CH <SEP> S <SEP> Clcrystalline <SEP> powder <SEP> H <SEP> 2, <SEP> 20 <SEP> H <SEP> 2 , <SEP> 39 <SEP> 366/38000 <SEP> X
<tb> <SEP> L / \ / \ <SEP> A <SEP> F = via <SEP> 300 <SEP> N <SEP> 12, <SEP> 25 <SEP> N <SEP> 12,

   <SEP> 27 <SEP> 305/17000
<tb> 102 / <SEP> C <SEP> I <SEP> GC <SEP> C /
<tb> <SEP> (o-dichlorobenzene) <SEP> (457, <SEP> 38) <SEP> M-G
<tb> <SEP> N-N <SEP> 0 <SEP> N-N
<tb> <SEP> 90, <SEP> 6 <SEP> light yellow, <SEP> fine, <SEP> C <SEP> 52, <SEP> 52 <SEP> C <SEP> 52, <SEP> 34 <SEP > 378/29900 '
<tb> <SEP> S <SEP> HC-CH <SEP> Sglärnzemdo <SEP> Blatt-H <SEP> 2, <SEP> 20 <SEP> H <SEP> 2, <SEP> 00 <SEP> 367 / 30000+
<tb> <SEP> / \ <SEP> II <SEP> 11 / \ <SEP> chenF = iiber300'N <SEP> 12, <SEP> 25 <SEP> N <SEP> 12, <SEP> 35 <SEP > 306/13000 +
<tb> 103 <SEP> Cl / \ <SEP> C <SEP> C-C <SEP> CrC <SEP> C / \ <SEP>.

   <SEP> Z'xichlorbenzol) <SEP> (457, <SEP> 38) <SEP> L-G
<tb> <SEP> N-N <SEP> O <SEP> NN
<tb> <SEP> HsCO <SEP> S <SEP> HC-CH <SEP> S <SEP> OCHs <SEP> 100 <SEP> Luminous, <SEP> bright-C <SEP> 58, <SEP> 91 < SEP> C <SEP> 58, <SEP> 92 <SEP> 381/40200 <SEP>
<tb> <SEP> / \ <SEP> II <SEP> II / \ <SEP> yellow, <SEP> fine, <SEP> ver-H <SEP> 3, <SEP> 60 <SEP> H <SEP> 3, <SEP> 65 <SEP> 369 <SEP>! <SEP> 40000 <SEP> X
<tb> 104 <SEP> cC <SEP> \, <SEP> Cl <SEP> felted <SEP> needle wires <SEP> N <SEP> 12, <SEP> 49 <SEP> N <SEP> 12, < SEP> 39 <SEP> 327/23600
<tb> <SEP> N-N <SEP> O <SEP> N-N <SEP> F = 291-291, <SEP> 8 <SEP> (448, <SEP> 53) <SEP> L-G
<tb> <SEP> (o-dichlorobenzene)
<tb> <SEP> H3CO <SEP> S <SEP> HC-CH <SEP> S <SEP> OCHs100 <SEP> Luminous, <SEP> bright-C <SEP> 58, <SEP> 91 <SEP> C < SEP> 58, <SEP> 76 <SEP> 377/38400
<tb> <SEP> yellow, <SEP> fine, <SEP> ver-H <SEP> 3,

   <SEP> 60 <SEP> H <SEP> 3, <SEP> 86 <SEP> 366/38200 <SEP> f
<tb> felted <SEP> needle <SEP> N <SEP> 12, <SEP> 49 <SEP> N <SEP> 12, <SEP> 44 <SEP> L-G
<tb> <SEP> N-N <SEP> O <SEP> N-N <SEP> F = 210-211, <SEP> 6 <SEP> (448, <SEP> 53)
<tb> <SEP> (chlorobenzene)
<tb>
EMI16.1


<tb> No. <SEP> Formula <SEP> Off properties <SEP> Analysis <SEP> Fluorescence <SEP> e.g.
<tb> <SEP> loot <SEP> calculated <SEP> found
<tb> <SEP> in <SEP> Vo <SEP> (Mol) <SEP> zmax / ±
<tb> <SEP> 100 <SEP> Luminous <SEP> yellow, <SEP> C <SEP> 58, <SEP> 91 <SEP> C <SEP> 58, <SEP> 91 <SEP> 384/41600)
<tb> <SEP> S <SEP> HC-CH <SEP> S <SEP> matted <SEP> needles H <SEP> 3, <SEP> 60 <SEP> H <SEP> 3, <SEP> 69 <SEP> 374/41500 <SEP>
<tb> / \ <SEP> 11 <SEP> 11 / \ <SEP> F = 262, <SEP> 4-264 '<SEP> N <SEP> 12, <SEP> 49 <SEP> N <SEP> 12 , <SEP> 75 <SEP> LG
<tb> <SEP> (o-dichlorobenzene) <SEP> (448, <SEP> (448,

  
<tb> <SEP> N-N <SEP> 0 <SEP> N-N
<tb> <SEP> 77, <SEP> 5 <SEP> Luminous <SEP> yellow, <SEP> C <SEP> 54, <SEP> 92 <SEP> C <SEP> 54, <SEP> 70 <SEP> 387/41500 <SEP> t
<tb> <SEP> HaCO <SEP> S <SEP> HC-CH <SEP> S <SEP> OCHa <SEP> fine, <SEP> matted <SEP> H <SEP> 4, <SEP> 25 <SEP> H <SEP> 4, <SEP> 32 <SEP> 376/40500 <SEP> J
<tb> L / \ <SEP> II <SEP> 11 / \ <SEP> A <SEP> needles <SEP> N <SEP> 9, <SEP> 82 <SEP> N <SEP> 9, <SEP> 89 <SEP> 333/24000
<tb> <SEP> F = 262, <SEP> 4-264 <SEP> (568, <SEP> 64) <SEP> S-G
<tb> <SEP> n <SEP> N-N <SEP> 0 <SEP> N-N <SEP> (o-dichlorobenzene)
<tb> <SEP> 89, <SEP> 2 <SEP> yellow, <SEP> fine-tone C <SEP> 47, <SEP> 98 <SEP> C <SEP> 47, <SEP> 84 <SEP> 392 / 37500
<tb> <SEP> HC-CH <SEP> S <SEP> HC-CH <SEP> S <SEP> HC-CH <SEP> stallinesPulver <SEP> H <SEP> 2, <SEP> 01 <SEP> H <SEP> 1,

   <SEP> 91 <SEP> 381/36600
<tb> 11 <SEP> 11 / \ <SEP> 11 <SEP> 11 / \ <SEP> 11 <SEP> 11 <SEP> F = 265-267'N <SEP> 13, <SEP> 99 <SEP> N <SEP> 13, <SEP> 98 <SEP> 332/20500
<tb> <SEP> \ / 11-11 <SEP> \ / 11 <SEP> 11 <SEP> \ / <SEP> (o-dichlorobenzene) <SEP> (400, <SEP> 53) <SEP> S-G
<tb> <SEP> S <SEP> N-N <SEP> 0 <SEP> N-N <SEP> S
<tb>
Example 7
6, 82 parts of the bis-diacylhydrazine of the formula (109),
EMI16.2
 (which can be prepared by reacting 2 moles of benzoyl chloride with 1 mole of thiophene-2,5 dicarboxylic acid dihydrazide in pyridine) 10 parts of phosphorus pentasulphide are added to 150 parts by volume of pyridine while stirring, the reaction mixture being heated.

   As soon as no further rise in temperature can be observed, the reaction mixture is brought to the boil over the course of 3 hours and stirred at a low boiling point for a further 18 hours.



  The mixture is cooled to room temperature, 50 parts by volume of ethanol and then 2000 parts of water are added in several portions, and the mixture is neutralized with an aqueous sodium hydroxide solution. After suction filtering, washing with cold and hot water and drying, the crude product is recrystallized from 350 parts by volume of o-dichlorobenzene with the aid of activated carbon. About 4.6 parts are obtained, corresponding to 68.3% of theory, 2- [5'-phenyl- (1 "') - 1', 3 ', 4'-thia diazolyl- (2')] - 5- [5 "-phenyl- (1" ") - 1", 3 ", 4" -thiadiazolyl- (2 ")] -thiophene of the formula
EMI16.3
 in the form of a light yellow powder that melts over 300.

   After recrystallizing twice from o-dichlorobenzene, a pale yellow, finely crystalline powder is obtained which fluoresces yellow under ultraviolet light.



  Analysis: C20H12N4S3 (404, 548) calculated: C 59, 38 H 2, 99 N 13, 85 S23, 78 found: C 59, 20 H 3, 10 N 13, 87 S 23, 81 1 UV absorption in dioxane: ? max = 381mÁ (e = 14800 *)? max = 370mÁ (? = 15000 *)
The table below describes a further 1, 3, 4 thiadiazole compounds which can be prepared according to the above procedure. The data on the yield relate to the crude product which has been recrystallized once. The e-values marked with + are uncertain because of the difficulty of the connections.

   The abbreviations in the column above fluorescence are the same as in Example 1.
EMI16.4


<tb>



  No. <SEP> Formula <SEP> Off-property <SEP> Analysis <SEP> Fluorescence
<tb> <SEP> loot <SEP> calculated <SEP> found
<tb> <SEP> in <SEP> / o <SEP> (Mol) <SEP> imax / e
<tb> <SEP> HsC <SEP> S <SEP> HC-CH <SEP> S <SEP> CH3 <SEP> 61, <SEP> 3 <SEP> Yellow, <SEP> shiny, <SEP> C <SEP > 61, <SEP> 08 <SEP> C <SEP> 61, <SEP> 04 <SEP> 379 <SEP>! <SEP> 37000
<tb> in <SEP> 11 <SEP> \ <SEP> C <SEP> C <SEP> CC <SEP> C / <SEP> short <SEP> needles <SEP> H <SEP> 3, <SEP> 73 <SEP> H <SEP> 3, <SEP> 74370/38500}
<tb> <SEP> II <SEP> II <SEP> \ / II <SEP> II <SEP> F = 291, <SEP> 2-292 <SEP> N <SEP> 12, <SEP> 95 <SEP> N <SEP> 12, <SEP> 97 <SEP> 270/10000
<tb> <SEP> N-N <SEP> S <SEP> N-N <SEP> (o-dichlorobenzene) <SEP> (432, <SEP> 60) <SEP> M-G
<tb> <SEP> 62, <SEP> 4 <SEP> golden yellow, <SEP> C <SEP> 61, <SEP> 08 <SEP> C <SEP> 60,

   <SEP> 94 <SEP> 385/26500 '
<tb> <SEP> S <SEP> HC-CH <SEP> S <SEP> short, <SEP> matted <SEP> H <SEP> 3, <SEP> 73 <SEP> H <SEP> 3, <SEP > 70 <SEP> 375/27000 +
<tb> Css <SEP> needle <SEP> N <SEP> 12, <SEP> 95 <SEP> N <SEP> 12, <SEP> 81. <SEP> 272/850 <SEP> (<SEP>? < SEP> +
<tb> <SEP> 112 <SEP> HS <SEP> N-N <SEP> F = about <SEP> 300 <SEP> (432, <SEP> 60) <SEP> St-G
<tb> <SEP> N-N <SEP> S <SEP> N-N <SEP> (trichlorobenzene)
<tb>
EMI17.1


<tb> No.

   <SEP> Formula <SEP> Off properties <SEP> Analysis <SEP> Fluorescence
<tb> <SEP> loot <SEP> calculated <SEP> found
<tb> <SEP> in <SEP> olo <SEP> (mol)
<tb> <SEP> 59 <SEP> yellow, <SEP> small, <SEP> C <SEP> 65, <SEP> 08 <SEP> C <SEP> 65, <SEP> 04 <SEP> 384/40500
<tb> 113 <SEP> HgC <SEP> S <SEP> HC-CH <SEP> 5 <SEP> C <SEP> Zende <SEP> H <SEP> 5, <SEP> 46 <SEP> H <SEP> 5, <SEP> 43 <SEP> 375/40800 <SEP> i
<tb> <SEP> I / \ <SEP> II <SEP> II / \ <SEP> plate <SEP> N <SEP> 10, <SEP> 80 <SEP> N <SEP> 10, <SEP> 84 < SEP> 275/11500
<tb> <SEP> H3C-C <SEP> C <SEP> CC <SEP> CC <SEP> C <SEP> C-CH3 <SEP> F = via <SEP> 3000 <SEP> (516, <SEP> 76) <SEP> St-G
<tb> <SEP> HsCN-N <SEP> S / N-N <SEP> CHa <SEP> W dichlorobenzene)
<tb> <SEP> 62 <SEP> bright yellow, <SEP> C <SEP> 62, <SEP> 58 <SEP> C <SEP> 62, <SEP> 48 <SEP> 380/28000 + t
<tb> <SEP> HsC <SEP> S <SEP> HC-CH <SEP> S <SEP> CHs <SEP> fine,

   <SEP> matted <SEP> H <SEP> 4, <SEP> 38 <SEP> H <SEP> 4, <SEP> 67 <SEP> 371/29000 +
<tb> <<SEP> Cj <SEP> Needle <SEP> N <SEP> 12, <SEP> 16 <SEP> N <SEP> 12, <SEP> 45 <SEP> 275/10500 +
<tb> <SEP> F = via <SEP> 300 <SEP> (460, <SEP> 66) <SEP> St-G
<tb> <SEP> N-N <SEP> S <SEP> N-N <SEP> (o-dichlorobenzene)
<tb> <SEP> Cl, <SEP> S <SEP> HC-CH <SEP> S <SEP> Cl <SEP> 59, <SEP> 5 <SEP> light yellow, <SEP> C <SEP> 50, < SEP> 74 <SEP> C <SEP> 50, <SEP> 44 <SEP> 370/17000 +
<tb> 115 <SEP> CC <SEP> CC <SEP> <<SEP> fine crystalline <SEP> H <SEP> 2, <SEP> 13 <SEP> H <SEP> 2, <SEP> 12 <SEP> St -G
<tb> <SEP> powder <SEP> N <SEP> 11, <SEP> 83 <SEP> N <SEP> 11, <SEP> 70
<tb> <SEP> N-N <SEP> S <SEP> N-N <SEP> F = via <SEP> 300 <SEP> (473, <SEP> 45)
<tb> <SEP> (trichlorobenzene)
<tb> <SEP> 42, <SEP> 2 <SEP> Hollgelbe, <SEP> gldn-C <SEP> 50, <SEP> 74 <SEP> C <SEP> 50,

   <SEP> 79 <SEP> 383/14000 +
<tb> <SEP> S <SEP> HC-CH <SEP> S <SEP> zende, <SEP> very <SEP> fine, <SEP> H <SEP> 2, <SEP> 13 <SEP> H <SEP > 2, <SEP> 30 <SEP> 372/14500 +
<tb> 116 <SEP> 11 <SEP> 11 / \ <SEP> verfmo <SEP> Nddel-N <SEP> 11, <SEP> 83 <SEP> N <SEP> 11, <SEP> 85 <SEP> 272 / 4900 +
<tb> <SEP> 116 <SEP> Cl <SEP> C-C <SEP> Cd <SEP>
<tb> <SEP> N-N <SEP> S <SEP> N-N <SEP> F = via <SEP> 300
<tb> <SEP> (trichlorobenzene)
<tb> <SEP> HsCO <SEP> S <SEP> HC-CH <SEP> S <SEP> OCHs <SEP> 40 <SEP> yellow, <SEP> fine <SEP> C <SEP> 56, <SEP> 87 <SEP> C <SEP> 56, <SEP> 57 <SEP> 385/42000 <SEP> t
<tb> <SEP> 117 <SEP> needle <SEP> H <SEP> 3, <SEP> 47 <SEP> H <SEP> 3, <SEP> 56 <SEP> 373/42000
<tb> F = 252-253, <SEP> 4 '<SEP> N <SEP> 12, <SEP> 06 <SEP> N <SEP> 11, <SEP> 93 <SEP> M-G
<tb> <SEP> \ - / II <SEP> II <SEP> \ / II <SEP> II
<tb> <SEP> N-N <SEP> S <SEP> N-N <SEP> (o-dichlorobenzene)

   <SEP> (464, <SEP> 60)
<tb> <SEP> OCHs <SEP> SHC-CH <SEP> S <SEP> OCH372, <SEP> 5Yellow, <SEP> giän-C <SEP> 56. <SEP> 87 <SEP> C <SEP> 57 , <SEP> 10 <SEP> 382/42200 <SEP> t
<tb> 118 / \ <SEP> C <SEP> C <SEP> GC <SEP> C / <SEP> zende, <SEP> fine <SEP> H <SEP> 3, <SEP> 47 <SEP> H < SEP> 3, <SEP> 71 <SEP> 372/42500 <SEP> $
<tb> <SEP> 11 <SEP> 11 <SEP> \ / ¯> <SEP> Pliittehen <SEP> N <SEP> 12, <SEP> 06 <SEP> N <SEP> 11, <SEP> 95 <SEP > 264/10500
<tb> <SEP> N-N <SEP> S <SEP> N-N <SEP> F = 244, <SEP> 4-245 <SEP> (464, <SEP> 60) <SEP> St-G
<tb> <SEP> (o-dichlorobenzene)
<tb> <SEP> 60, <SEP> 3 <SEP> yellow, <SEP> very <SEP> C <SEP> 56.

   <SEP> 87 <SEP> C <SEP> 56, <SEP> 86 <SEP> 377/14000 +
<tb> <SEP> S <SEP> HC-CH <SEP> S <SEP> one, <SEP> matted <SEP> H <SEP> 3, <SEP> 47 <SEP> H <SEP> 3, <SEP > 59 <SEP> LG
<tb> 119 <SEP> H3COt <SEP> G / C <SEP> C <SEP> C <SEP> {/ Ce <SEP> OCHs <SEP> little needles <SEP> N <SEP> 12, <SEP> 06 < SEP> N <SEP> 12, <SEP> 24
<tb> <SEP> 119I <SEP> ICO \ / <SEP> I <SEP> II <SEP> \ - / F = over <SEP> 300 <SEP> (464, <SEP> 60)
<tb> <SEP> N-N <SEP> S <SEP> N-N <SEP> (trichlorobenzene)
<tb> <SEP> HsCO <SEP> S <SEP> HC-CH <SEP> S <SEP> OCHs <SEP> 68, <SEP> 8 <SEP> yellow, <SEP> fine-C <SEP> 54.

   <SEP> 94 <SEP> C <SEP> 55, <SEP> 01 <SEP> 393/38500
<tb> 1 <SEP> CC <SEP> <<SEP> crystalline <SEP> H <SEP> 3, <SEP> 84 <SEP> H <SEP> 3, <SEP> 80 <SEP> 382/39000 <SEP >
<tb> <SEP> -% <SEP> II <SEP> II <SEP> \ / II <SEP> II <SEP> \ - / powder <SEP> N <SEP> 10, <SEP> 68 <SEP> N <SEP> 10, <SEP> 49 <SEP> SS-G
<tb> <SEP> N-N <SEP> S <SEP> N-N <SEP> F = 231, <SEP> 2-234, <SEP> 8 <SEP> (524, <SEP> 66)
<tb> <SEP> (o-IDichlorobenzene)
<tb> <SEP> S <SEP> HC-CH <SEP> S <SEP> 61, <SEP> 5 <SEP> yellow, <SEP> fine-C <SEP> 66, <SEP> 64 <SEP> C <SEP> 66, <SEP> 35 <SEP> 393, <SEP> 139000
<tb> 121 <SEP> gC /% <SEP> crystalline <SEP> H <SEP> 3, <SEP> 20 <SEP> H <SEP> 3, <SEP> 17 <SEP> 382/39200
<tb> <SEP> 121 <SEP> 4 <SEP> \ <SEP> 5 <SEP> 11 <SEP> lCI49 <SEP> powder <SEP> N <SEP> 11, <SEP> 10 <SEP> N <SEP > 11, <SEP> 07 <SEP> MG
<tb> <SEP> N-N <SEP> S <SEP> N-N <SEP> F = via <SEP> 300 <SEP> (504,

   <SEP> 67)
<tb> <SEP> (trichlorobenzene)
<tb> <SEP> HC-CH <SEP> S <SEP> HC-CH <SEP> S <SEP> HC-CH <SEP> 65, <SEP> 2 <SEP> yellow, <SEP> fine-C < SEP> 49, <SEP> 98 <SEP> C <SEP> 49, <SEP> 89 <SEP> 395/44000 <SEP> 1
<tb> 11 <SEP> 11 / \ <SEP> 11 <SEP> 11 / \ <SEP> 11 <SEP> 11 <SEP> crystalline <SEP> H <SEP> 2, <SEP> 10 <SEP> H < SEP> 2, <SEP> 85 <SEP> 384/43400 <SEP> X
<tb> <SEP> 122 <SEP> II <SEP> \ / II <SEP> II <SEP> \ / Puler <SEP> N <SEP> 14, <SEP> 57 <SEP> N <SEP> 14, < SEP> 68 <SEP> 284/13500
<tb> <SEP> O <SEP> N-N <SEP> S <SEP> N-N <SEP> O <SEP> F = via <SEP> 300 <SEP> (384, <SEP> 47) <SEP> none
<tb> <SEP> (o-dichlorobenzene)
<tb>
EMI18.1


<tb> No. <SEP> Formula <SEP> Off properties.

   <SEP> analysis <SEP> fluorescence
<tb> <SEP> loot <SEP> calculated <SEP> found
<tb> <SEP> in <SEP> / o <SEP> (mol) <SEP> max <SEP> e
<tb> <SEP> HC-CH <SEP> S <SEP> HC-CH <SEP> S <SEP> HC-CH <SEP> 74, <SEP> 6 <SEP> yellow, <SEP> glossy-C < SEP> 46, <SEP> 13 <SEP> C <SEP> 45, <SEP> 85 <SEP> 398/20000 +
<tb> <SEP> II <SEP> 11 / \ <SEP> 11 <SEP> 11 / \ <SEP> 11 <SEP> 11 <SEP> zende, <SEP> fine <SEP> H <SEP> 1, < SEP> 94 <SEP> H <SEP> 1, <SEP> 93 <SEP> 382/20200 +
<tb> 123 <SEP> HC <SEP> zC-IC <SEP> Cw <SEP> platelets <SEP> N <SEP> 13, <SEP> 45 <SEP> N <SEP> 13, <SEP> 67 <SEP > MG
<tb> <SEP> \ / II <SEP> II <SEP> \ / II <SEP> II <SEP> \ /
<tb> <SEP> S <SEP> NN <SEP> S <SEP> NN <SEP> S <SEP> F = via <SEP> 300 <SEP> S <SEP> 38, <SEP> 49 <SEP> S <SEP> 38, <SEP> 29
<tb> <SEP> (o-dichlorobenzene) <SEP> (416, <SEP> 60)
<tb>
Example 8 12,

   73 parts of the bis-diacylhydrazine of the formula
EMI18.2
 (which can be prepared by reacting 2 moles of furoyl chloride with 1 mole of terephthalic acid dihydrazide in pyridine) are mixed with 20 parts of phosphorus pentasulfide in 150 parts by volume of pyridine with stirring, the reaction mixture heating up. As soon as no further rise in temperature can be observed, the reaction mixture is brought to the boil over the course of 21/2 hours and stirred at a low boiling point for a further 20 hours. It is cooled to room temperature, 50 parts by volume of ethanol and then 2000 parts of water are added in several portions, and the mixture is neutralized with aqueous sodium hydroxide solution.

   After suction filtering, washing with cold and hot water and drying, about 12.4 parts, corresponding to 98.1 / o of theory, 1- [5'-furyl- (2 "') - 1', 3 ', 4' -thiadiazolyl- (2 ')] - 4- [5 "-furyl- (2" ") - 1", 3 ", 4" -thiadiazolyl- (2 ")] benzene of the formula
EMI18.3
 obtained in the form of a yellowish powder that melts over 300. After three recrystallization from o-dichlorobenzene, 5.2 parts, corresponding to 41.1 / o of theory, of a pale yellowish, finely crystalline powder are obtained.



   Example 9 polyacrylonitrile fabric, e.g. B. ¸Orlon¯, at a liquor ratio of 1:40 with 0.1% 2- [pyridyl- (4 ')] - 5- [4 "-tert. Butylphenyl- (1")] - 1, 3, 4-thiadiazole of the formula (8) treated for one hour at about 70 to 97 in a bath which contains 1 g of 85% formic acid per liter. Then the material is rinsed and dried. The fabric obtained in this way has a higher whiteness content than the untreated material.



   If, instead of the 2- [pyridyl- (4 ')] - 5- [4 "-tert.Butylphenyl- (1")] - 1,3,4-thiadiazole, an equal amount of 2- [pyridyl- (4') ] -5- [3 ", 4" -dimethylphenyl (1 ")] - 1, 3, 4-thiadiazole of the formula (9), a similar optical brightening effect is obtained.



   Example 10
From a 10 "/ o strength acetyl cellulose solution in acetyl which, calculated on the acetyl cellulose, is 1 / o 2- [3 ', 5'-dimethyl-thienyl-2')] -5, [4" -tert. butylphenyl- (1 ")] - 1, 3, 4-thiadiazole of the formula (83) and 2- [3 ', 5' dimethyl-thienyl- (2 ')] - 5- [3", 4 "-dimethoxyphenyl- (1 ")] - 1, 3, 4-thiadiazole of the formula (89), films of approximately 40 µ thick are produced.

   After drying, the following values are obtained for the transmission of ultraviolet light (measured with a Beckmann-DU spectrophotometer): Light transmission 1, 3, 4-thiadiazole analysis: C18H10O2N4S2 (378.44) calculated from the formula: C57.13 H2, 66 N14.81 (83) (89) found: C 57, 18 H 2, 86 N 14, 89 00 / o at ¯320-360 ¯320-380 mÁ zozo at 376, 5,390, 5 m, u UV- Absorption in dioxane: 10% at 379 393 mÁ? Max = 364mÁ (@ = 50200)} 25% at 382.5 396.5 mÁ? Max = 355mÁ (@ = 50100) 50% at 387.5 400.5 mÁ? max = 273mÁ (@ = 8400) 75% at 395 ¯405 mÁ

 

Claims (1)

PATENT CLAIM Process for the production of new 1, 3, 4-thiadiazoles of the formula EMI19.1 wherein Rt, R2 and Rg are aromatic or heterocyclic radicals, at least one of these radicals being heterocyclic, and n being an integer not exceeding 2, characterized in that acylhydrazines of the formula EMI19.2 with phosphorus sulfides. SUB-CLAIMS 1. Process according to patent claim, characterized in that the starting materials used are acylhydrazines whose heterocyclic radicals Ri and or R2 contain a five- to six-membered ring with a heteroatom as the only ring. 2. The method according to claim, characterized in that the starting materials used are acylhydrazines whose heterocyclic radicals Ri and / or R2 are pyridine, furan or thiophene radicals. 3. The method according to claim, characterized in that acylhydrazines are used as starting materials, the aromatic radicals Rl and / or R2 contain 1 to 2 aromatic six-membered rings. 4. The method according to claim, characterized in that the starting materials used are acylhydrazines whose radicals R3 are benzo radicals. 5. The method according to claim, characterized in that the starting materials used are acylhydrazines whose radicals Rg are furan or thiophene radicals. 6. The method according to claim, characterized in that the reaction is carried out in the presence of a tertiary nitrogen base.