DE1298096B - Process for the production of cyanamides from cyanazide and organic compounds - Google Patents

Description

Temperature between 25 and 15O ⁰ C, preferably io chloride with either an alkali metal or ammonium Between 40 and 100 ⁰ C, if appropriate in the presence of azide as described above, to produce. Solutions,

which contain about 20 to 40 percent by weight of cyanazide, however, are because of safety and convenient handling preferred. Because of the rela-

an inert reactant.

The pressure applied is not essential
Its significance and, depending on the volatility of the reactants, is generally 15 tive instability of the cyanazide if it is generated at atmospheric or slightly elevated pressures. best either in the presence of the saturated,

The aliphatic or cycloaliphatic compound necessary to carry out the reaction Time varies from a few minutes with very reactive or in the presence of a reactant. In which capable compounds up to several hours or the latter method are given to the saturated, aliphatic longer with less reactive compounds. 20 tables or cycloaliphatic reactants If desired, the course of the reaction can be through to the reactant which is the previously prepared Measuring the amount of nitrogen evolved tracks containing cyanazide. Alternatively, one can be the cyano azide; For each converted cyanazide molecule, solution is also given to the reactant. 1 molecule of nitrogen set free. As starting materials for the inventive method

The process in the process according to the invention is any saturated, monomeric, aliphatic cyanazide, N ₃ CN, if it is free or almost free from solvent or static or cycloaliphatic compounds, explosive and should be bar.

be handled with great care. One can In general one uses the organic verbines but with relative certainty when used with cyanazide in essentially equimolar amounts dilute 30 parts of a thin or moderately concentrated solution, but one or the other can also

Reactants are present in excess.

If the saturated, aliphatic or cycloaliphatic compound is a liquid under the reaction conditions, it can be used both as a reaction flask with a condenser, thermometer, magnetic medium and as a reactant, stirrer, gas inlet tube and nitrogen bubble counter Reagent, so equipped, is dried in the flame and
cooled to room temperature under nitrogen. Man
gives 16.25 g (0.25 mol) sodium azide and 48.5 g (62.5 ml)
add dry acetonitrile and cool the flask 40 to be substantially inert. It goes without saying, therefore, that in an ice-salt bath at -10 to 0 ^° C. Ice water or a coolant is passed through the coolant in each individual case
- 5 to 0 ⁰ C and distilled with good agitation
20 ml (24.0 g, 0.39 mol) of cyanochloride with such
Speed in the flask so that a temperature of 45 amide, 1,1,2,2-tetrachloroethane, isooctane, methylene below 12 ° C is maintained. After chlorine, carbon tetrachloride and 1,2-dibromomethane. end of the addition, stir the mixture The reaction between cyanazide and saturated,

V ₂ hours at 0 to 10 ⁰ C and then aliphatic or cycloaliphatic compounds can be slowly heated to room temperature within one hour at temperatures above 50 ° C. Although at this point the reaction of a carbon-hydrogen bond with nitrogen is essentially complete, the mixture can be precipitated and bonded with a

turn around.

The cyanazide to be used in the reaction can be prepared beforehand or in situ. In the former Trap can be made as follows: A 125 ml

it should normally be liquid and when applied Reaction temperature towards the reactants and reaction products in the

must select the reaction conditions used. Suitable reactants are propionitrile, Acetonitrile, ethyl acetate, amyl acetate, dimethylform

Cyanamide group is formed, e.g. B. according to the following reaction scheme:

(R ¹ HR ² J (R ³ JCH + N ₃ CN

> (R ¹ J (R ² J (R ³ JC-NHCN + N ₂ T

stir overnight at room temperature, excess cyanogen chloride is removed by about 1 hour evacuation through the cooled cooler (0 ⁰ C) at a pressure of 95 to 120 mm, wherein 55 is stirred. The solution remaining in the flask is filtered under nitrogen and the filter cake is washed twice with a total of 10 ml of dry material

Acetonitrile. The combined filtrate (67 to 72 ml), where R is hydrogen, halogen, nitro, cyano, consists of a solution of cyano azide in acetonitrile, 60 alkoxy, acyl, acyloxy, carboxyl, carbamoyl, can be used immediately or under nitrogen at a store group or optionally substituted with one or ⁰ -20 C for later use. several of the above-mentioned groups sub-

Cyanazide is shock-sensitive and means up to a defined alkyl or cycloalkyl radical, i.e. not thermally stable to a certain extent. Its a haloalkyl, nitroalkyl, cyanoalkyl, alkoxy solutions in organic solvents, e.g. B. aceto- 65 alkyl-, halocycloalkyl-, nitrocycloalkyl-, cyanitrile, ethyl acetate or toluene, but are in space cycloalkyl or alkoxycycloalkyl radical, each temperature stable for several days and individual of these radicals can contain up to 18 carbon atoms at temperatures below 0 ° C stored indefinitely and R ¹ with R ² , R ² with R ³ or R ¹ with R ³

together can represent alkylene having 2 to 7 carbon atoms. Cyanazide decomposes accordingly at around 50 ° C the reaction scheme in nitrogen and cyanitrene,: N - CN, which then has a carbon-hydrogen bond reacted.

The saturated, monomeric, aliphatic or cycloaliphatic reactants include cy- _ clopropane, cycloheptane, cyclohexane, cyclooctane, decahydronaphthalene, nitrocyclohexane, chlorocyclohexane, Cyclohexanecarboxylic acid, cyclohexanecarbonitrile, bicyclo- [2.2, l] -heptane, methane, propane, isooctane, Dodecane, nonadecane, octadecane, 2,4,4-trimethylpentane, 1-nitrooctane, 2-chloropropane, tert-butyl chloride, Ethyl acetate, octylacetaJ, 1,4-dicyanobutane, sebacic acid, butyramide, dioxane, tetrahydrofuran, Diethyl ether, ethylene glycol dimethyl ether and methyl ethyl ketone.

The cyanamides obtainable by the process of the invention can depending on the number the - CH sites that take part in the reaction with cyanazide, one or more cyanamide groups, d. H. - contain NHCN groups, the free bond of which is directly bonded to the carbon atom, originally bonded to the hydrogen atom that migrated to form the cyanamide group was.

Some of the products obtained from saturated, aliphatic or cycloaliphatic monomers are new and some already known.

As illustrated in Example 13, reaction products which can be prepared by the process of the invention are useful as laminating adhesives, especially for glass-on-glass surfaces.

As shown in Example 14, alkaline hydrolysis of the compounds which can be prepared is obtained is, amines, these are compounds with known uses.

example 1

A suspension of 6.0 g of sodium azide and 50 ml of cyanochloride is stirred overnight at reflux temperature.

100 ml of 2,3-dimethylbutane are added and the excess cyanochloride is removed under pressure of 200 mm and room temperature. Filtration of the remaining suspension through a glass frit Nitrogen gives a colorless filtrate, which one diluted to 310 ml by adding 2,3-dimethylbutane.

At 21 hours of stirring, this solution at 49 to 5O ⁰ C, a total of 1720 ml (85%) nitrogen develop removed mm excess hydrocarbon at 40 ° C and a pressure of. 5 The remaining, slightly orange-colored oil is then placed in a flask for molecular distillation and distilled at 0.03 μ with a bath temperature of 40 to 65 ° C. The result is a distillate amount of 4.30 g (40%).

2217 cm " ¹ (C = N). The CMR spectrum was found to correspond to a mixture of 1: 8.3" 1-cyanamide-2,3-dimethylbutane and 2-cyanamide-2,3-dimethylbutane .
5

Example 2

The procedure of Example 1 is essentially repeated and η-hexane is added with cyano azide around. The product is a viscous liquid which, in 53% yield, consists of a mixture of isomers 1 -Cyanamid-hexane and the new 2- and 3-Cyanamidhexanen in a ratio of 1: 6: 6 contains. These Isomers show lines in the ultrared spectrum

3180cm- ¹ (NH) and 2200cm "- ¹ (C = N).

Analysis for C ₇ H ₁₄ N ₂ :

Analysis for C ₇ H ₁₄ N ₂ :

Calculated ... C 66.72, H 11.20, N 22.23;
found .... C 66.82, H 11.13, N 22.46.

The ultrared spectrum shows characteristic bands at 3205 cm " ¹ (NH), 2890 cm" ¹ (CH) and

Calculated ... C 66.71, H 11.1, N 21.9;
found .... C 66.37, H 11.08, N 22.97.

Example 3

The procedure of Example 1 is essentially repeated and 2,2-dimethylbutane is added Cyanazide around. A viscous liquid is obtained which contains a mixture in 65% yield which consists of the new isomers 1-, 3- and 4-cyanamide-2,2-dimethylbutane in an approximate ratio of 1: 4: 1 consists. These isomers show in the ultrared spectrum

Lines at 3210 cm ^-1 (NH) and 2210 cm ^-1 (C = N).

Example 4

The procedure of Example 1 is essentially repeated and methylcyclohexane is reacted with cyanoazide. A viscous liquid is obtained which contains the five new isomers, 1-cyanamide-methylcyclohexane, 1-cyanamide-1-methylcyclohexane and the corresponding 2-, 3- and 4-methylhexanes in a yield of 30%. These isomers show lines at 3190 cm " ¹ (N-H) and 2210 cm" ¹ (C = N) in the ultrared spectrum.

Analysis for C ₈ H ₁₄ N ₂ :

Calculated ... C 69.57, H 10.15, N 20.31;
found .... C 69.26, H 10.17, N 21.30.

Examples 5 to 12

In the following table a number of additional experiments are summarized under Use of the procedure and amount of reactants given in Example 1 carried out were, but with the modification that instead of the starting material in Example 1 2,3-dimethylbutane used uses the hydrocarbon indicated in the left column. The physical properties given in the right column come from the crude reaction products. In Examples 10 and 11, the weight ratio of cyclohexane to the other is Hydrocarbon 3: 1, and in Example 13 the amount of bicyclo [2,2,2] octane used is so great that one has a saturated cyclohexane solution at ambient temperature.

5 yield
(%) Ultra red '
(cm " ¹ ) 6th example Raw material 80 3200 Ν -
2210 C = N Physical Properties 5 Cyclopentane 67 3200 N-H
2210 C = N viscous liquid 6th Cyclooctane 55 viscous liquid 7th Methylcyclopentane 45 3200 N-H
. 2210 C = N 8th 1,1-dimethylcyclohexane 77 3210 N-H viscous liquid 9 Cyclohexane 2210 C = N viscous liquid Cycloheptane 50 3200 N-H 10 Cyclohexane 2200 C = N viscous oil 2,2,33-T-tetramethylbutane 50 3200 N-H 11 Cyclohexane 2210 C = N viscous oil Bicyclo- [2.2.1] -heptane 44 3180 Ν --Η 12th Cyclohexane 2210 C = N viscous oil Bicyclo [2.2.2] octane

example

H ₂

H,

H ₂ C CH ₂ H ₂ C CH ₂ -N-CN

II + N ₃ CN »II + N ₂

H ₂ C CH ₂ H ₂ C CH ₂

H ₂

0.07 mol of cyanazide, prepared from sodium azide and cyanochloride in cyclohexane, is freed from Excess cyanochloride by evacuating to 110 to 120mm / 25 ° C and filtered to make sodium chloride to remove. The filtrate is diluted further with cyclohexane to a total volume of 300 ml and heated for 22 hours at 40 to 45 C; during this time approximately 0.06 moles of nitrogen are in Freedom set. The solution is filtered to remove an extremely small amount of insoluble residue separate, and remove the excess cyclohexane in a rotary evaporator at 2 mm / 40 C. It remains an essentially pure cyclohexylcyanamide (5.68 g, 65% yield) as a light brown oil. If you distill this light brown oil in a Short-path distillation apparatus at 0.01 μ at a bath temperature of 90 to 114 ° C., 'is obtained in this way pure cyclohexylcyanamide (4.58 g, 53% yield) as a light brown oil.

Analysis for C ₇ H ₁₂ N ₂ :

Calculated ... C 67.68, H 9.75, N 22.57;
found .... C 67.76, H 9.74, N 22.60 ..

The ultrared spectrum agrees with the assumed structure, which shows an absorption at 3.15 μ (NH), 3.42, 3.50 μ (saturated C -Η bond) and 4.5 μ (CN). The CMR spectrum shows a double bond at τ 4.2, 4.33 (NH); a broad absorption band lies around τ 6.96 (proton bound to NH — CN), and a broad complex lies between τ 7.70 and 9.20 μ (CH ₂ ) in a ratio of 1: 1:10. The identification of cyclohexylcyanamide is confirmed by hydrolyzing it to cyclohexylurea as follows: 50 ml of water are added to 5.0 g (0.04 mol) of cyclohexylcyanamide prepared in the same way as described above and 20 drops of 10 ° sulfuric acid. The mixture is gradually heated to 72 ^° C. within 2 hours; at this temperature the oily product turns into a white, crystalline solid. The heating is continued at 64 to 72 ^° C. for 1 hour. The solution is cooled, filtered and the white crystals are dried over P ₂ O ₅ at 67 ° C / 0.1 mm and 4.65 g of a product with a melting point of 194 to 195 ° C. is obtained. Another 0.9 g ( mp 192-194 ⁰ C) is separated by concentrating the filtrate from (overall yield. 97.5%). Recrystallization from water gives analytically pure cyclohexylurea which melts at 195 to 196.degree.

Analysis for C ₇ H _W N ₂ O:

Calculated ... C 59.10, H 9.93, N 19.71;
found .... C 58.98, H 10.23, N 19.68.
C 58.85, H 10.06.

The mixed melting point of this compound with a known sample of cyclohexylurea shows no humiliation.

A thin film of the cyclohexylcyanamide prepared as above is placed between two glass plates. The structure is then heated for 3 to 4 minutes at 180 to 250 ° C. On cooling, a clear, firm bond between the plates. Correspondingly strong bonds between glass surfaces are obtained.

55

by mixing a mixture of cyclohexylcyanamide with either 1,6-hexamethylenedicyanamide or with Adipic acid nitrile used and 18 hours at 180 ° C hardens.

Example 14

/ f \
+ N ₃ CN->

L-N-CN

9.75 g (0.15 mol) of activated sodium azide are suspended in 30 ml of methylene chloride and the mixture is cooled to 0.degree and within 30 minutes adds 40 ml of cyanochloride at such a rate that a temperature below 12 C is maintained. When the addition is complete, the solution is left slowly warm to room temperature and continue stirring for 20 hours at this temperature. 100 ml of methylene chloride are added and the solution is evacuated to 400 mm at 20 ° C. to remove any excess Remove cyan chloride. The mixture is filtered and the filtrate (86 ml) is analyzed Cyano azide (yield 78%). 13.6 g (0.1 mol) of adamantane are added and the solution is heated for 48 hours 34 to 37 C; during this time approximately 0.08 moles of nitrogen are released. By filtering 0.1 g of an insoluble material is separated from this solution. The filtrate is to dryness evaporated and the residue slurried with carbon tetrachloride. The soluble fraction is chromatographed one on silica. The main crystalline fraction is eluted with 50 to 30 "chloroform in carbon tetrachloride. Recrystallization from methylcyclohexane gives 1-cyanamidadamantane with a melting point of 147 to 149 C (1.25 ti. Yield: 7%).

Analysis for C _n Hu ₁ N ₂ :

Calculated ... C 74.95. H 9.15, N 15.90:
found .... C 75.20, H 9.08. N 15.68.

In addition, 5.05 g (37 "") of adamantane is obtained return.

Hydrolysis of this material gives 1-aminoadamantane. 0.88 g (5.0 mmol) of 1-cyanamidoadamanian. which was prepared as above, and 1, (X) g (25 mmol) Sodium hydroxide is dissolved in 5 ml of diethylene glycol and heated under reflux with stirring for 2 hours. The product is cooled to room temperature. pour it into a saturated potassium carbonate solution and extracted with ether. The ether is dried with anhydrous potassium carbonate, filtered and evaporated him off. The oily residue is sublimed: a product is obtained whose ultra-red spectrum corresponds to the of a known 1-aminoadamantane sample.

B e i s ρ i e 1 15,

OO

N ₃ CN + (CH ₃ I ₃ C - Cl - * (CHj) ₂ C - Cl + N,

40 13.6 g (0.2 mol) of cyanazide, dissolved in acetonitrile (total volume of the solution 115 ml), are added to 442 (4.8 mol) of t-butyl chloride, and the solution is stirred for 17% for ₂ hours Heated at 52 to 54 C. During this time about 0.2 moles of nitrogen are released. The reaction mixture is filtered to remove a small amount of insoluble material and the filtrate is evaporated to dryness on a rotary evaporator at 1 mm / 25 ° C. 16.10 g of a mobile, light brown oil remain. The ultra-red spectra of this oil show absorption at 3.0, 3.2, 3.3 μ (NH, CH) and 4.4 to 4.6 μ (CN). The product decomposed during the distillation (0.5 μ, 85 to 1 IOC pot temperature) and gave a small amount (3.1 g) of an unidentified oil and a brown, amorphous residue.

Example 16 O O

N ₃ CN +

C-OH

C-OH

CH, NHCN 13.9 g (0.22 mol) of cyanazide in acetonitrile dissolved (total volume of the solution 125 ml), added to 28.1 g (0.22 mol) of cyclohexanecarboxylic acid, and that Mixture is stirred at 50 bis for 17 hours 59 C heated, during which time about 0.17 mol of nitrogen are released. The reaction mixture is filtered to separate a light yellow powder (12.4 g). The filtrate becomes dry at 1 mm / 30 ° C evaporated. 27.10 g of a mobile, light brown oil remain. The ultra-red spectrum of this oil show the absorption characteristic of the expected product [3.1 μ (NH), 3.4, 3.5 μ (C - H). 4.4. 4.6 µ (CN)]. Additional absorption at 5.5 μ leaves suspect that other products were formed. By simple distillation under reduced Pressure (1 μ), the pure cyanamide cannot be separated from unreacted cyclohexanecarboxylic acid.

Claims (2)

Patent claims: 1. Process for the preparation of cyanamides from cyanazide and organic compounds, thereby marked that one saturated, aliphatic or cycloaliphatic compound represented by nitro. Cyano, alkoxy, acyl, Acyloxy, carbonyl, carbamoyl groups or halogen atoms can be substituted and the contains at least one hydrogen atom bonded to carbon, with cyanazide at a temperature between 25 and 150 ° C., preferably between 40 and 100 ° C., optionally in the presence an inert reactant. 2. The method according to claim 1, characterized in that the reaction is carried out with in miu Cyanazide formed performs. 909 526 399