DE1041495B - Process for the preparation of dihydrodicyclopentadienylamine - Google Patents

Description

It has been found that the previously unknown dihydrodicyclopentadienylamine can be obtained by dihydrodicyclopentadienyl isothiocyanate is hydrolyzed either with formic acid or with zinc and hydrochloric acid reduced or treated dicyclopentadiene directly with sulfamic acid.

Dihydrodicyclopentadienylamine is thus formed by hydrolysis of the dihydrodicyclopentadienyl isothiocyanate obtainable from dicyclopentadiene through prolonged exposure to organic acids, especially formic acid, in the heat. The response times are between 5 and 300 hours. The formic acid withdrawn can be used for further reactions if of 90 to 100% acid is assumed. By treating the reaction product with alkali, shaking out with a suitable solvent, e.g. B. trichlorethylene, and subsequent distillation becomes dihydrodicyclopentadienylamine obtained in yields of up to 80%.

Furthermore, dihydrodicyclopentadienylamine is formed in the reduction of dihydrodicyclopentadienyl isothiocyanate with zinc and aqueous hydrochloric acid in alcohol.

One can also start from dicyclopentadiene by using it to develop HSCN with a rhodanide and formic acid and the resulting reaction product (mustard oil) immediately, without separation, then hydrolyzed with formic acid.

Finally, dihydrodicyclopentadienylamine is formed in the direct reaction of dicyclopentadiene with Amidosulfonic acid and / or related compounds.

Dihydrodicyclopentadienylamin is as acetyl and benzoyl identified (mp. 135-136 ° C and 160-162 ⁰ C). The reaction with nitrite in 20% acetic acid at 60 ° C leads to oxydihydrodicyclopentadiene, which is identified as a phenyl urethane with a melting point of 162 ° C. Dihydrodicyclopentadienylamin and phenyl isothiocyanate to give N-phenyl-N-dihydrodicyclopentadienylthioharnstoff mp. 160, which is also available from Dihydrodicyclopentadienylisothiocyanat and aniline to 161 ⁰ C. The reaction product from Dihydrodicyclopentadienylamin and Dihydrodicyclopentadienylisothiocyanat agrees with that obtained by alkaline hydrolysis of Dihydrodicyclopentadienylisothiocyanat bis (dihydrodicyclopentadienyl) thiourea of mp. 219-220 ⁰ C. The latter compound, which is obtained from Dihydrodicyclopentadienylamin and CS _2, is a mixture of diastereoisomers.

Dihydrodicyclopentadienylamine can be split into optical antipodes with α-tartaric acid as follows: Dihydrodicyclopentadienylamine is taken up in a hot aqueous solution of α-tartaric acid. Upon rapid cooling, a uniform looking salt separates into processes of manufacture
of dihydrodicyclopentadienylamine

Applicant:

Farbwerke Hoechst Aktiengesellschaft
ίο formerly Master Lucius & Brüning,
Frankfurt / M., Brüningstr. 45

Dr. Randolph Riemschneider, Berlin-Charlottenburg,
has been named as the inventor

splendid needles which, according to analysis, represent the hemihydrate of the acid tartrate. When cooling slowly however, in three approaches with varying amounts of water, d-tartaric acid, dihydrodicyclopentadienylamine a more difficultly soluble part in the form of hexagonal plates and prisms and a more easily soluble part in the form fibrous needles obtained.

When breaking down the two salts with caustic soda and absorbing the free, optically active forms of the Dihydrodicyclopentadienylamine in trichloromethane turns the amine obtained from the less soluble plates on the other hand than that obtained from the more easily soluble fraction (needles).

The new process product is suitable for. B. as an intermediate for chemical syntheses, e.g. B. for the Production of quaternary ammonium bases.

The dihydrodicyclopentadienyl isothiocyanate, for its preparation protection within the scope of the present invention is not claimed, z. B. can be produced as follows:

a) 297 g (2.25 mol) of dicyclopentadiene are converted into 600 ecm of concentrated formic acid in a 2-1 three-necked flask (98 to 100%) and 20 g of KSCN added.

The mixture is then heated to 95 ° C. in the course of 10 minutes with vigorous stirring and reflux cooling on a water bath. Both dicyclopentadiene and formic acid change color from yellow to brown. 7 g of KSCN are then added every 3 minutes for a total of 322 g (3.33 mol) in 2% hours. After the mixture has been kept under the specified conditions for 1 hour, it is cooled to room temperature and stored for _{2 days.} The initially still existing gas evolution in the formic acid leaves

809 659/426

3 4

gradually after. The top mustard oil layer is used in Example 1

Separated separating funnel (399 g), filtered again hydrolysis of dihydrodicyclopentadienyl

and directly from a 1-1 flask over the asbestos mesh isothiocyanate with formic acid

distilled. 96 grams (0.5 moles) of dihydrodicyclopentadienyl isothiocyanate

The yield of Dihydrodicyclopentadienylisothio- 5 are with 300 ml of 95 ° / ₀ formic acid in a

Cyanate crude product without volatile impurities 1-1 three-necked flask under reflux for 25 to 30 hours

is 318 g. heated in the boiling water bath while stirring. Included

b) 264 g (2.0 mol) of pure, freshly distilled dicyclo- hydrogen sulfide develops (blackening of pentadiene will be in a 500 ccm three-necked flask, the lead acetate paper at the end of the cooler). Then it is still with a dropping funnel, intensive condenser, which carries a normal pressure suction device for 15 hours without stirring on the boiling water bath for the hydrocyanic acid formed, filtered (0.5 to 1 g solid, black residue) and is provided with a stirrer, on the boiling and the brown, clear liquid on the water bath warmed up with water bath. A freshly prepared solution is ^{concentrated from 35 to 40 °} C. in a water jet vacuum. 152 g (2.0 mol) of NH ₄ SCN in 80 ecm of water remain - 90 ecm of a brown syrup which adds 400 ecm and vigorously stirred until a fine distribution of water is diluted, with a milky cloudiness occurs, the organic phase has entered. In the course of under reflux, 100 g of solid sodium hydroxide 2 ¹ J ₂ hours are entered at 95 ° C 225 ecm concentrated and, while cooling the flask by aqueous hydrochloric acid, added dropwise to the extent that a position in a water bath and swirling to the solution rapid distribution in Mixture brought by immediate detection. This separates from the stirring vortex above the aqueous phase. After the acid 20 has been introduced, a dark brown oil is produced. After cooling, the mixture is stirred at 95 ° C. for a ^{further 1} l for _{2 hours.} Mixing to 25 ° C, the oil is triturated with 250 to 325 ecm

The reaction mixture, cooled to 70 ° C., is taken up by chloroethylene, the trichloroethylene layer is suctioned off through an acid-resistant filter, 8 g of oil-moist iso-iso separated in a separating funnel and remaining with 50 ecm of trichloroperthiocyanic acid. Ethylene washed after suction. The combined Trichloräthylenwird the filter residue with 5 ecm ethanol and 10 ecm 25 solutions are dried with sodium sulfate and washed on trichlorethylene and added to the filtrate 390 ecm the water bath, towards the end of the distillation at 95 ° C distilled trichlorethylene, which the organic and a pressure of 15 mm Hg. Phase is then taken up. The phases are then separated in a separator - the crude amine on an oil bath at 15 mm Hg in a stick funnel, and the organic phase is distilled off twice, each time using a stream of material. A glassy 450 ecm 2% bicarbonate solution and three times with 30 each solidifying black-brown residue remains in the flask.
500 ecm of water was washed again, whereby in addition to salts and pentadienylamine at bp ₁₅ 109 to 111 ° C., the pure dihydrodicyclo acids also passed over during the redistillation. It is a will. The trichlorethylene phase is shaken with dehydrated, water-white, very characteristic smelling liquid sodium sulfate until it becomes clear, this lower viscosity than dihydrodicyclopentadienyl is removed by suction filtration and 15 ecm trichloro isothiocyanate. Washed by ethylene when placed in a cold bath. The trichlorethylene is ^{solidified at -5O 0} C dihydrodicyclopentadienylamine rapidly a pressure of 25 mm Hg and 40 ⁰ C water bath and becomes crystalline after trituration. The pure dihydrodite temperature is deducted, then at a pressure of cyclopentadienylamine the more volatile impurities can easily be removed without turbidity in 2 nH Cl 12 mm Hg. After standing for several weeks in a sealed distilled bottle, the temperature of the bath gradually turns pale yellow and should be increased to boiling point. then higher-boiling components that are no longer in different

The yield of dihydrodicyclopentadienylisothio- dilute aqueous HCl are soluble. Raw product:

cyanate crude product without more volatile constituents yield 59 g; pure product: yield 53 g. The benzoyl

is 323 g. derivative of dmydrodicyclopentadienylamine melts at

The crude dihydrodicyclopentadienyl isothiocyanate becomes 45 160 to 162 ° C.

from a 750 cc flask at a pressure of 20 to ^ ₁ C ₁₇ H ₁₉ ON (molecular weight 253.3):

25 mm Hg to 220 m a ⁰ C heatable oil bath destd- * ^{"v 19 °;}

lates. The boiling capillary is regulated in such a way that uncalculated N- 5.52 / ₀ ;

broke a relatively strong flow of air through the oil pearls. rounded M - 5.47 J ₀ .

There is a great tendency to delay boiling and show 50 The acetyl compound of dihydrodicyclopentadienyl

men. A gradual increase in the boiling point of the amine melts at 135 to 136 ° C.

at 150 ° C. gives 32 g of a continuously boiling 4.5 g (0.03 mol) of dihydrodicyclopentadienylamine are intermediate fraction. It has a specific Rho in a 100 ccm flask with 20 g of acetic anhydride odor and turns red _{with FeCl 3.} At fraktio-sets. Heating occurs when mixing. After distillation ned are in it dicyclopentadiene and 55 the mixture detectable ¹ _J2 hour on the asbestos network under re-Dihydrodicyclopentadienylisothiocyanat. With flow and calcium chloride completion in gentle boiling continued distillation, dihydrodicyclopenta has been kept, the acetic anhydride on the dienyl isothiocyanate is distilled off at a pressure of 22 mm Hg and a water bath in a water jet vacuum, 173 to 175 ° C as a pale yellow oil. Multiple is enhanced vacuum to 15 mm Hg and the product observations still in the process in the cooler a white, amorphous product 60 ¹ Z ₂ hours on a boiling water dried respects, the in organic solvents and dihydro- After cooling the flask to room temperature and dicyclopentadienylisothiocyanat is itself insoluble and grinding the oily residue solidifies in crystalline form. Finally, the latter is separated off by filtration. The acetyl compound of the dihydrodicyclopenta distillation flask is located in a black, highly viscous dienylamine, quantitatively as a dry, white crystal residue, which masses before further heating in a vacuum. The acetyl derivative is decomposed three times from methanol with smoke formation and recrystallized glassy on cooling: melting point 135 to 136.degree.
stiffens. It is soluble in pyridine, somewhat soluble in hot
Nitrobenzene. Analysis C ₁₂ H ₁₇ ON (molecular weight 191.3):

Yield of pure dihydrodicyclopentadienyliso- Calculated N = 7.32 ^ ₀ ;

thiocyanate 285 g (75% of theory); Kp. _Fi 140 to 142 ° C. 70 found N = 7.51%.

Example 2

Reduction of dihydrodicyclopentadienyl isothiocyanate with zinc and hydrochloric acid

11.4 g (0.06 mol) of dihydrodicyclopentadienyl isothiocyanate are dissolved in 60 ecm of ethanol by heating on a water bath under reflux. 60 g of zinc dust are then added and the mixture is cooled to such an extent that dihydrodicyclopentadienyl isothiocyanate just remains in solution. In the course of 2 hours, 50 ecm of concentrated aqueous hydrochloric acid is added in small portions. The temperature during the reduction is 0 to 5 ° C., during which H ₂ S evolution can be observed in larger amounts (detected with lead acetate paper). The Nutsche excess zinc dust contains an admixture of trimeric thioformaldehyde (sublimation from 150 ⁰ C, mp. 213-215 ° C). It is washed with 10 ecm of ethanol-ether (1: 1). After treating the filtrate with 30% aqueous potassium hydroxide solution, an alcoholic brown phase separates out on top (separated in a separating funnel, the lye is washed twice with 20 ecm of ethanol each time). The combined alcohol components are subjected to distillation under N ₂ on the asbestos network. An initially weakly, from about 100 ° C strongly alkaline liquid distilled over, which consists of ethanol, water, dihydrodicyclopentadienylamine and by-products. It is then evaporated to dryness (residue including KOH, KCl); the temperature in the tower is Anschiitz least 22O ⁰ C. The highest boiling fraction (150 to 220 ⁰ C) results in cooling of two layers, which no longer mix homogeneously. The higher boiling point shows the characteristic odor of dihydrodicyclopentadienylamine.

The entire distillate is strongly acidified with HCl with cooling. After concentrating on the water bath a white, somewhat greasy residue remains until dry, in which prisms become closed under the microscope are recognizable. The main mass melts around 200 ° C, and from around 190 ° C there are subliming ones up to 250 ° C infusible needles. The crystal mass is taken up in 5 ecm of water, filtered and with 3 ecm Aqueous 10% potassium hydroxide solution made alkaline, with cloudiness, amine odor and the formation of two phases. According to the rules of the Schotten-Baumann reaction, 2 g of benzoyl chloride are added and the pale yellowish, solid deposit sucked off. Recrystallization takes place twice from a little methanol, from which the benzoyl derivative of dihydrodicyclopentadienylamine is allowed to crystallize out in colorless skewers: mp. 160 up to 162 ° C. Mixed melting point with the preparation obtained under a) 160 ° C.

The dihydrodicyclopentadienyl isothiocyanate obtained from dicyclopentadiene by the action of formic acid on a rhodanide can also without isolation directly, as described above, to dihydrodicyclopentadienylamine, that is, in one step, to be implemented.

Example 3

Implementation of dicyclopentadiene with amido and
Diamidosulfonic acid

a) 6.6 g of dicyclopentadiene, 4.85 g of amidosulfonic acid, 3 g of diamidosulfonic acid, 50 g of ammonia and toluene are heated in a pipe for a long time. When the reaction is complete, ammonia will evaporate brought and treated the reaction product with hot water. The amine can be removed from the organic phase isolate as usual. The yield is 70% of theory.

The dihydrodicyclopentadienylamine is converted into the benzoyl derivative with a melting point of 160 to 162 ° C (see example 1).

b) The procedure is as above. The addition of ammonium salts and urea favors the implementation. The amine is obtained in good yield. The amine is identified as an acetyl derivative from melting point 135 to 136 ° C.

The reaction of dicyclopentadiene with the specified additives can also take place in an aqueous medium.

Claims (2)

Patent claims: 1. Process for the preparation of dihydrodicyclopentadienylamine, characterized in that one Dihydrodicyclopentadienyl isothiocyanate is either heat hydrolyzed with formic acid or reduced with zinc and hydrochloric acid at 0 to 5 ° C or dicyclopentadiene directly with sulfamic acid and or or related compounds. 2. The method according to claim 1, characterized in that a dihydrodicyclopentadienyl isothiocyanate is used as the starting material used, which is made from dicyclopentadiene, a rhodanide and formic acid and from which the dihydrodicyclopentadienyl isothiocyanate was not isolated. Considered publications:
U.S. Patent No. 2,395,455. © 809 659/426 10.5S