DEP0053415DA - Process for the preparation of 1, 2, 3-triazole derivatives. - Google Patents

Description

^ j '· - -ν. , j " Li. O. üU

BASISCHE ANILII- & SOUA-FABHIK (I ₈ (J ₀ JParbenin.dustrie Aktiengesellschaft »In Dissolution»).

Our reference: Q ₉ Z ₆ 1 ^ 4-59 A.

Ludwigahafen (Rh), August 29, 1949 Et / R,

'26. June 1950 Et / Schr,

ρ 53 415 IYc / 12 ρ D.

Process for the production of Y-triazole derivatives o

It has been found that new triazole derivatives are obtained if alcohols of the acetylene series or theirs by conversion of the oxy group are used Reacts available derivatives with organic derivatives of hydrazoic acid »

Suitable starting materials are, on the one hand, propargyl alcohol, 2-butynol- (l), phenylprop & rgjrlalkohol, 2-butynediol- (1.4-), hexadiyne- (2.4) -diol- (1.6) and their alkyl ethers, and also the esters of Alcohols with carboxylic or sulfonic acids or with hydrogen halides, so zJ. the 1,4-dichloro-butyne- (2) j on the other hand Zc3 ₀ the methyl, ethyl, cyclohexyl or

C.
Bienylazid, the /.ampherazid ,, Azidotetrazol, Azidoazobenzol, Azidoantipyrin, .Azidokaffein, Azidosuccinäureester or Azidophenylarsönsäuren =

The reaction generally takes place rapidly and practically completely when approximately equivalent amounts of the components are heated, The azide group is expediently deposited in a solvent on the triple bond of the acetylene alcohol, and mono- and bis-oxyalkyl derivatives are obtained from the acetylene alcohols of triazoles. "

The triazole derivatives are wertvollri intermediates, z "B ₀ for pharmaceuticals"

The parts given in the examples are 3 weight parts

Example 1;

119.1 parts phenyl azide ogh ₅ N ₅ are 69.4 parts Z- butynediol (1.4) in about 160 parts of isobutanol, 5 hours

The reflux condenser heated to a gentle boil = the alis-crystallizing l = »phenyl-4 <.5-'bis-oxymethyl-triazole on cooling the formula

C ₆ H ₅ -HQ-CH ₂ OH

N G-GH ₀ OH

% ²

is aspirated and aas water with the addition τοη animal charcoal, umkristallisierto It forms colorless prisms, mp 157-159 ° t _s slightly soluble in hot iVasser in alcohol and acetone * in kaltemfWasser, Zther and benzene, however, are difficult to dissolve, "The yield of pure product is about $ 80 the amount calculated on butynediol.

Example 2 \

A solution of 58 parts of propargyl alcohol and 119 * 1 parts of phenylaside in 50 parts of isobutanol is used for 5 hours The reflux condenser is heated to the boil »After cooling, a product crystallizes in atm esg d <*« »Ρίο, which after the Recrystallization from aqueous ethyl alcohol at 107 to 109 ° melts? and that the formula

CJEL • -N CH C ₆ Hc ^ -K C-CH ₉ OH

⁶ 5 j ρ or ^{b 5} j | ^ά

HC - CH ₅ OH H CH

belongs "It is i $ helssem water and Xn most organic means leight soluble? hardly soluble in cold water and petrol »

Example J, ι

If, as in the preceding examples, 110 parts of hexadiinjdiol (l _e 6) are reacted with 245 parts of phenyl azide in 200 parts of isobutanol, a product with a melting point of 202 to 2049 _t which presumably has the constitution is obtained after the liquid components have been removed by steam

HO CH ₂ - Cr = G - Q = ZQ - - CHg - OH

'Ν

comes to. It is sparingly soluble in water and benzene, in alcohol and glacial acetic acid in the "heat easily soluble" The yield is about $ 70 of theory »

Example 4 «

294 parts of the 2-butynediol (Ie4) dibenzoyl compound from Schmjjo 76 _S 5 ° and 125 parts of phenyl azide are dissolved in 200 parts of toluene and the mixture is refluxed for 7 hours. The volatile components are then distilled off with steam and the residue is recrystallized from alcohol. A dibenzoyl compound having a melting point of 86 to 87 ° _f which is identical to the dibenzoyl compound which is conventionally obtained by benzoylating the compound is obtained in about 50% yield 1-Phenyl-4,5-Ms-oxymethTl-triazoles prepared according to Example 1 can win.

Example 5 °

A solution of 223 parts of 4-azidoazobenzene and 90 parts of 2-butynaiol- (14) in alcohol is refluxed for 6 hours. On cooling, fine, orange-red needles of 4a5-Bi3-oxymethyl-lj ^ f ^ are obtained '- _/ ^ henylazophenyl-) triazole- (1.2.3) of the formula

from zeroing point 199 - 200 °. The yield "entered 83fo the theory ο

Example 6 _O

74 parts of 3-butynol- (2) are boiled with 250 parts of 4-nitrophenyl azide in alcohol for several hours. The 4- or "5-ox, y ^ thyl-l - (4 ^f - ^ itrophenyl) -ytriazole- (l < ₁ 2", 3) of the formula are obtained in 72% yield

A C-CH (OE) -CH ₅ or ßE

The new compound forms pale yellowish crystals with a melting point of 151 - 153 ° _s which dissolve moderately in water and easily in alcohol _e

Bj5JJ3 £ ij} i_Z £.

202 parts of ~ N- (4-azidophenyl-) - pyrrolidone- (2), which is used in

Claims (1)

218-220 ° forms «, the yield is about can be prepared from N- (4-aminophenyl-) - pyrrolidone ~ (2) and the cream-colored, light-decomposable leaflet of Melting point 7 ° -60 ° is boiled with 90 parts of 2-butynediol- (l «4) alcohol for several hours Yield a triazole derivative of the formula ^ J ₆ H ₄ -NG-CH ₂ OH ² jj N G-CH ₀ OH which forms pale yellowish needles of decomposition point 216-218, which are soluble in alcohol and in alcohol _{If 74 parts of 3-butynol- (2) f} are used instead of 2-butynediol ~ (lo4), a corresponding pyrrolidinophenyloxyethyltriazole is obtained which dissolves in alcohol, colorless, glossy flakes that are less soluble in water and have a decomposition point The bulge
Example 8, A solution of 24.3 parts of 4-azidophenylarsic acid and 9 parts of 2-butynediol (l.:4) in alcohol is refluxed for 6 hours then heated on the water bath, the alcohol is evaporated on the descending condenser and the residue is crystallized from water with the addition of some animal charcoal to «The resulting compound of the formula BOCH ₂ -Q
UP ₂ - forms fine, pale yellowish needles which are fairly easily soluble in water and very easily soluble in alcohol =, you begin yourself to discolor at about 180 ° and char at higher temperatures without melting «, the yield is 63 $ of theory. Pat e nt ans ρτ uch: ^ i $ ~ J * s Process for the production of triazole derivatives by reacting acetylene derivatives with derivatives of hydrazoic acid, characterized in that alcohols of the acetylene series or their obtainable by converting the oxy groups Derivatives with organic derivatives of hydrazoic acid BADISGHE ANILINE & SODA FACTORY fr.