DE1944429A1 - Tertiary formamide prepn pesticide or plant - protector - Google Patents

Abstract

Tertiary formamides, useful as plant protective agents and pesticides or as raw materials for their synthesis, have formula R2R3N-CHO (where R2 and R3 are formyl, CL2CH- or opt. F- or phenyl-substd. 1,2,2,2-tetrachlorethyl or 1,2,2,3,3,3-hexachloropropyl groups). They are prepared by reacting tertiary formamide chlorides Cl2CHN(CHCl-R1)CHCl-R (where R and R1 are Cl or opt. F- or phenyl- substd. 1-2C perchloralkyl) with anhydrous HCOOH at 0-100 degrees C.

Description

New tertiary formamides The invention relates to new tertiary formamides Formamides and a process for their preparation.

It is known that tertiary amide chlorides at higher temperatures very easily decompose into imide chlorides and alkyl chlorides (3er.37, 2678, 2812 (1904)).

It has now been found, surprisingly, that hitherto unknown tertiary formamides are obtained if tertiary formamide chlorides of the general formula are used in which R and R1 are identical or different, where R and R1 stand for chlorine or a perchlorotalkyl radical optionally substituted by fluorine or a phenyl group and having 1 or 2 carbon atoms, is reacted with anhydrous formic acid.

It is preferably in the temperature range from about 0 to about 1000.degree 20 to 1900 C, in particular 40 to 900 C worked.

In general, one goes in the implementation of the tertiary formamide chlorides with anhydrous formic acid in such a way that the reaction components are in a molar ratio mixes from about 1: 1 to 1:10 at room temperature. After the immediately subsided The onset of elimination of hydrogen chloride will complete the reaction Heated to a maximum of 100 ° C. until the evolution of hydrogen chloride ceased.

If 2 or 3 N-dichloromethyl groups are present in the molecule, then the reaction can also be carried out in stages.

The calculated amount of anhydrous is then added Formic acid at about 20 to 300, whereby after the introduction of the 2nd or 3rd .. formyl group is then heated to a maximum of 100 ° a. For transferring all b-dichloromethyl groups in formyl groups can also be used directly with excess formic acid at 20 to 300 C added and after the evolution of hydrogen chloride, which began immediately, had subsided be heated to a maximum of 1000 C to complete the reaction.

The reactions can also be carried out using an inert solvent such as chloroform or carbon tetrachloride.

If, for example, tris (dichloromethyl) amine or N-dichloromethyl-N, N-bis (1,2,2,2-tetrachloroethyl) amine are used as starting materials for the process according to the invention, the reaction can be controlled by the the following formula schemes are reproduced: It is surprising that the chlorine atoms of the N-chloromethyl groups are not attacked. The new tertiary formamides were purified by recrystallization, sublimation or distillation.

The chlorinated tertiary foreamide chlorides used as starting material are also new and, according to an older proposal of our own, can be obtained by chlorinating tertiary formamides with phosgene and chlorine. Examples include: tris (dichloromethyl) amine, N-dichloromethyl-N, N-bis (1,2,2,2-tetrachloroethyl) amine, N-dichloromethyl-N, N-bis- (1,2 , 2,3,3,3-hexachloropropyl) amine, N, N-bis (dichloromethyl) -N- (1,2,2,2-tetrachloroethyl) amine The compounds that can be prepared according to the invention are new and correspond to the general formula wurin R2 and R3 are identical or different, where R2 and R3 represent the formyl, dichloromethyl or a 1,2,2,2-tetrachloroethyl or 1,2,2,3,3, optionally substituted by fluorine or the phenyl group, 3-hexachloropropyl group.

The new tertiary formamides are valuable Auaganga products for the synthesis of herbicides and pesticides and show themselves to be effective in these areas.

The effectiveness is the example of the N, N-bis (1,2,2,2-tetrachloroethyl) formamide the formula (CCl3CHCl) 2N-CHO described. The compound is fungicidal. For example the mycelial growth of Piricularia oryzae, Phialophora cinerescens, Cercospora musae and Fusarium dianthi prevented at 50 ppm active ingredient concentration.

Also the others obtainable by the process according to the invention Compounds show a comparable effect.

The temperature data in the examples relate to Celsius.

Example 1 21 g of tris (dichloromethyl) amine are introduced into 50 ml of anhydrous formic acid with stirring. The mixture is then stirred for 12 hours at room temperature, the tris (dichloromethyl) amine going into solution with rapid evolution of HCl. Fractional distillation gives 10 g (81%) of the compound of the formula from Kp. @e: 87-89 °, n20D: 1.5028.

Analysis: CsHsCl2NO2 (molecular weight 155.9) calc. C 23.10 H 1.92 N 8.97 but. 23.5 2.0 9.2 Example 2 79.5 to 5 g of tris (dichloromethyl) amine are mixed with 120 ml of anhydrous formic acid. The mixture is stirred for 2-3 hours at 20-30 ° and then heated to 90-100 ° for 4-5 hours. The excess formic acid is stripped off in vacuo and the colorless crystalline residue is stored in a desiccator over caustic potash. The cleaning is done by sublimation at 70-80 ° (bath) / 0.05 Torr. 22 g (73%) of the compound of the formula are obtained of m.p. 92-94 °.

Analysis: CSHsNOs (molecular weight 101) mol. Wt. 113 Ber. C 35.64 H 2.97 N 13.86 Found 35.4 3.2 14.2 Example 3 59 g of N-dichloromethyl-N, N-bis (1,2,2,2-tetrachloroethyl) amine are with 75 ml of anhydrous formic acid for 2 hours at 20-30 ° and 2 hours at 80-90 ° stirred. Fractional distillation gives 43 g at 1100 / 0.15 Torr (48%) of the compound of the formula (CCl3CHCl) 2N-CHO was obtained. From petroleum ether (30-50 °) colorless crystals from m.p.

66-68 °.

Analysis: C5H3Cl8NO (molecular weight 376) boron. C 15.93 H 0.79 Cl 75.04 N 3.72 found 16.1 0.8 75.1 3r8 Example 4 30 g of N-dichloromethyl-N, N-bis (1,2,2,3,3,3-hexachloropropyl) amine are reacted analogously to Example 3 with 60 ml of anhydrous formic acid. 24 g (88%) of the compound of the formula (CCl3CCl2CHCl) 2N-CH0 with a melting point are obtained. 131-133 °.

Analysis: C7H3Cl12NO (molecular weight 542.4) calc. C 15.48 H 0.55 Cl 78.43 N 2.58 Gef. 15.8 0.9 78.5 2.5 The use for the method according to the invention Finding tertiary formamide chlorides have been obtained as follows: In the solution 146 g (2 mol) of dimethylformamide in 400 ml of chloroform are passed at 20-300 C 4 to 5 hours of phosgene in a rapid stream. Then under UV irradiation each until the end of the chlorine uptake 12 hours at 40-60 ° C and approx. 30 hours at 80-1000C chlorinated. The crystal sludge is sucked off from liquid components and that Washed crystals with petroleum ether.

Crude yield: 300 g of tris (dichloromethyl) amine.

After recrystallization from carbon tetrachloride or mineral spirits the colorless, hard crystals melt at 171 - 1730 C.

101 g (1 mol) of diethylsormamide are dissolved in 150 ml of CHCl3 and 4 Phoagened at 20-300 C for hours. Under intensive UV irradiation is then in each case 10 hours at 40-60 ° C, 15 hours at 80 ° C until the chlorine uptake ceases and chlorinated at 90-100 ° C for 20 hours.

The refractive index nD20 increases from 1.4335 (diethylformamide) to 1.5665; Raw yield: 410 g.

In the subsequent fractionation, the dichloromethyl-bis-tetrachloroethylamine goes at 134-1370 C / 0.02 torr above; nD20 = 1.5664.

97 g of di-n-propylformamide are phosgenated in 100 ml of chloroform for 3 1/2 hours at 10-200C. Then, under UV irradiation, chlorination is carried out for 10 hours at 40-60 ° C., 15 hours at 60-800 ° C. and 60 hours at 100-110 ° C. (nD20 = 1.5840) in each case until the end of chlorine uptake. The colorless liquid solidifies after some time to a pulp of crystals; Raw yield: 430 g. After recrystallization from light gasoline / white gasoline (1: 1), the colorless crystals of the formula melt at 143-1440 C; Pure yield: 160 g.

Claims (3)

Patent claims: 1¾ Tertiary formamides of the general formula where R2 and R3 are identical or different, where R2 and R3 are formyl, dichloromethyl or a 1,2,2,2-tetrachloroethyl or 1,2,2,3,3,3 optionally substituted by fluorine or phenyl group -Hexachiorpropyl group mean. 2) Process for the preparation of tertiary formamides, characterized in that one tertiary formamido chlorides of the general formula in which R and R1 are identical or different, where R and R1 represent chlorine or a perchloralkyl radical optionally substituted by fluorine or a phenyl group and having 1 to 2 carbon atoms, is reacted with anhydrous formic acid. 3) Method according to claim 2, characterized in that one is in the temperature range works from 0 to 1000 C.