DE2157454A1 - 1-AMINOMETHYL-ACENAPHTHENE AND THE METHOD FOR MANUFACTURING IT - Google Patents

Description

Our reference : OZ 27 807 WB / Be 6700 Ludwigshafen, 18.11.1971

1-Aminome thy! -Acenaphthene and process for their preparation

The invention relates to 1-aminomethyl-acenaphthenes and processes for their preparation by reacting 1-IOrmyl-acenaphthen with amino compounds and a reducing agent.

It is from Rodd, Chemistry of Garbon Compounds, Volume III B. (Elsevier Publ. Co., N.Y., 1956), p. 1462, it is known that Acenaphthenes hydrogenated in the presence of nickel to a mixture of 9,1,2,3-tetrahydroacenaphthene and decahydroacenaphthene will. Corresponding end products result from a reduction with sodium and boiling amyl alcohol. Ulimanns also teaches Encyklo-. pedie of technical chemistry (Urban and Schwarzenberg, Munich, 1953), Volume 3, Page 1 that acenaphthene provides the aforementioned hydrogenated products by catalytic hydrogenation.

It has now been found that 1-Aminomethy! Acenaphthene the general! formula

I,

in which R ^ and R _{2 can be the} same or different and each represent a hydrogen atom, an aliphatic, araliphatic, -cycloaliphatic ^ aromatic radical, in addition R ₁ also an amino group, hydroxy group, alkylamino group, the radical Rz-SOp-, where R ^ an aliphatic or aromatic

Means remainder, or the remainder R.

-C-N ^, in which the radicals R "

0 ^R 4

can be the same or different and each have a hydrogen atom, denote an aliphatic or aromatic radical, 172/71 - 2 -

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can mean, or IL and Rp also together with the "neighboring" Nitrogen atom can stand for members of a heterocyclic ring, is advantageously obtained when 1-FormyIacenaphthen the formula

OHC

II

with amino compounds of the general formula

R ₁ -

III,

wherein R ^ and Rp have the aforementioned meanings, and one Reducing agent converts.

The implementation can be used for the pail of I-Formylacenaphtheü and dimethylamine by the following formulas reproduce:

OHC

+ H ₂ O.

In view of the prior art, the process according to the invention surprisingly provides a large number of 1-aminomethylacenaphthenes in a simple way in good yield and purity. Products hydrogenated on the acenaphthene nucleus are formed not in significant quantities.

The starting material II is in a known manner, e.g. after

in the German patent specification (patent application

P 20 64 279.9) described method by reacting acenaphthene with carbon oxide and hydrogen in the presence of Rhodium catalysts. The starting material III becomes

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in. Stoichiometric amount, or in excess, advantageously in a ratio of 10 to 1.5 mol of starting material III per mole of starting material II. Preferred starting materials III and correspondingly “preferred end materials I” are those whose formulas with 2 to 10, in particular 2 to 6 carbon atoms, an alkylcarbonyl radical with 2 to 6 carbon atoms, an cyclohexyl radical, a cyclopentyl radical, an cycloheptyl radical, a cyclooctyl radical, an aralkyl radical with 7 to 12 carbon atoms, a phenyl radical, above in addition R ^ also an amino group, hydroxy group, alkylamino group with 1 to 4 carbon atoms or the radical R ^ -SO ₂ -, where R ~ is an alkyl radical with 1 to 6 carbon atoms or a phenyl radical

means, or the remainder R.

-C-UX / »where the radicals R. are the same

0 ^K 4

or can be different and each denotes a hydrogen atom, an alkyl radical having 1 to 4 carbon atoms or a phenyl radical, or R-. and Rp also together with the adjacent nitrogen atom for members of a 5-, S- or 7-membered, heterocyclic ring which, in addition to the nitrogen atom, also contains a further nitrogen atom or an oxygen atom or a keto group and to which a 5- or 6-membered, alicyclic ring can be fused, can stand. The radicals and rings mentioned can also be substituted by G groups which are inert under the reaction conditions, for example alkyl groups, acyloxy groups, alkoxy groups, alkylamino groups each having 1 to 4 carbon atoms, dialkylamino groups having 2 to 8 carbon atoms, carbalkoxy groups having 2 to 6 carbon atoms. '"· ■

For example, the following raw materials are used: III in embossing: Ammonia, methyl, dimethyl, diethyl-i, isobutyl, tert-butyl, sec-butyl, η-butyl, n-propyl, isopropyl, methoxypropyl, 2-ethyl-hexyl-, allyl-, butyn- (2) -yl-, di-n-propyl-, diisopropyl-, Ethyl, di-n-butyl, diisobutyl, N-methyl-F-butyl, Dodecyl, acetyl, propionyl, n-pentanecarbonyl, ß- (acetyloxy) -

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ethyl-, ß-ethylamino-ethyl-, γ-dimethylamino-propyl-, .ß-carbon ethoxy-ethyl, Cyclohexyl, cyclopentyl, benzyl, p-toluyl, 2,4-xylylamine, aniline, N-methylaniline, hydrazine, phenylhydrazine, N, N'-diethy! Hydrazine, hydroxylamine, N-ethy! -Hydroxylamine, 2-hydroxylaminobenzoic acid methyl ester; Ethylsulfonyl, phenylsulfonyl, p-toluylsulfonyl-amine; Urea, ethyl, dimethyl, Diphenyl, trimethyl urea; Pyrrolidine, 3,3-dimethylpyrrolidine, Piperidine, 3-methy! Piperidine, 2-methy1-5-ethy! Piperidine, Decahydroquinoline, morpholine, piperazine, F-methylpiperazine, 2,6-dimethylmorpholine; Hexamethyleneimine, 4-methy! Hexamethyleneimine, γ-aminobutyric acid lactam.

The reaction is generally carried out at a temperature of O "to 250 ⁰ C, preferably from 50 to 190 ⁰ C, without pressure or under pressure, continuously or discontinuously. If appropriate, used under the Heaktionsbedingungen inert solu-. Solvent such as water, in particular as a solvent for the starting material III; alkanols, for example methanol, ethanol, n-butanol; ethers such as diethyl ether; cyclic ethers such as tetrahydrofuran or dioxane.

The preferred reducing agent is hydrogen, as a rule in the presence of a hydrogenation catalyst, in embossing. Preferred Hydrogenation catalysts are generally one or more metals with an atomic number between 24 and 29, as a rule Cobalt, copper, manganese and / or nickel catalysts, e.g. corresponding sintered catalysts. The metals can also be used in the catalyst in the form of their oxides and / or in a mixture with phosphoric acid are present. Catalytic converters of the type mentioned contain between 3 and 30% by weight of copper, 0.5. and 10 wt Manganese and 10 and 80 wt. $ Cobalt or nickel, add to this optionally 0.1 to 5 wt. ^ Phosphoric acid, based on the Amount of metal.

The hydrogenation catalyst is usually used in the reaction in an amount of 5 to 30 wt. ^, Based on starting material II, used. It can be used in a mixture with a carrier material suitable for the reaction, e.g. silicon dioxide, wherein the amount of the catalyst is expediently 10 to 40 wt. $ of the mixture of catalyst and support, j-

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As a rule, such amounts of hydrogen are added to the reaction mixture at the beginning and in the course of the reaction that a corresponding reaction pressure, expediently between 150 and 300 atm, is always established at the reaction temperature. The reaction is generally carried out batchwise or continuously at a temperature between 80 and 200 ^° C., preferably between 120 and 190 ° C. Inert gases such as nitrogen can also be used to adjust the pressure accordingly.

Cobalt or nickel sintered catalysts, which can contain up to 30% by weight of copper, manganese, iron and / or chromium, are also advantageous; preferably Raney nickel and Raney cobalt are used. Such hydrogenation catalysts are usually added in amounts of 0.5 to 50% by weight, based on starting material II. Hydrogen is used in excess, based on starting material II. The reaction takes place at a reaction pressure between 50 and 300 atm, continuously or discontinuously; the reaction temperature is between 20 and 120 ^° C., preferably between 50 and 90 ^° C.

The reaction can also be carried out in the presence of palladium and / or its compounds, generally in an amount of 0.01 to 5 wt. $, Preferably 0.1 to 2 wt. $ Palladium as finely divided metal and / or calculated as palladium in Perform shape of its finely divided compounds, based on starting material II. Thus, for example as isomerization ^(catalysts palladium black, palladium powder, palladium, arsenide, cyanide, chloride, nitrate, iodide, oxide, sulfide, sulfate or complex salts such as TetracBorpalladate, Tetraamin- or Diaminpalladiumchloride, Hexachlorpalladate used The catalysts mentioned can advantageously also be applied in a known manner to supports , for example activated carbon, barium sulfate, silica gel or zeolites, and such supported catalysts can be used for the isomerization. Such supported catalysts can be prepared in any desired manner, eg by impregnating the support with appropriate solutions of the palladium salts by kneading or mixing while grinding the components

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of catalysts, especially supported catalysts, reference is made to Houben-Weyl, Methods of Organizational Chemistry, Volume 4/2, pages 137 ff. In a corresponding manner, platinum and / or its compounds, for example platinum oxide, can also be used as hydrogenation catalysts. The reaction is carried out with hydrogen, expediently in an amount of from 1 to 50, preferably from 5 to 25, mol, based on starting material II. The hydrogen can be fed continuously or discontinuously to the reaction and / or the contact itself can be reloaded freshly with hydrogen after a certain reaction time. It sets the starting material II in the - usually at a temperature between 20 and 200 ⁰ G, preferably between 50 and 150 C, under atmospheric or superatmospheric pressure, for example up to 50 at to.

Another advantageous reducing agent is formic acid, which is reacted in an amount of from 1.5 to 10, preferably from 2 to 4, mol, based on starting material II. The reaction is generally carried out at a temperature between 80 and 120 ^° C., preferably between 90 and 110 ^° C., without pressure or under pressure.

The reaction can be carried out as follows: A mixture of starting material II, starting material III and reducing agent, optionally together with hydrogenation catalyst and / or solvent, is for 4 to 24 hours, preferably in the case of hydrogen as the reducing agent from 6 to 12 and in the case of formic acid as reducing agent from 6 to 24 hours at the reaction temperature and optionally kept the aforementioned reaction pressure. The end product is then converted from the reaction mixture in the usual way, e.g. by fractional distillation, separated. -In the case of formic acid As a reducing agent, the reaction mixture is expediently mixed with alkali lye and heated, and the organic solution formed The binary mixture phase is separated off and the end product is isolated from it by fractional distillation.

The end product I is preferably isolated in the form of its salts, by, for example, the distillate of the reaction mixture,

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optionally in solution with an abovementioned solvent, reacted with the corresponding acid. Inorganic or organic Salts of the end product I come into imprinting, especially salts of hydrohalic acids such as hydrogen chloride and hydrogen bromide and hydrogen iodide, salts of sulfuric acid, phosphoric acid and organic salts. Acids such as maleic acid, succinic acid, Oxalic acid, tartaric acid, benzoic acid, citric acid, acetic acid, • formic acid.

In a further, expedient embodiment of the method the starting material II is first reacted with the starting material III and the so-formed Schiff base without separation reacted from the reaction mixture with the reducing agent. The aforementioned conditions are expediently maintained in both stages with regard to the proportions of the reaction components, temperature and pressure. In general, the aforementioned Total residence time used, the first stage suitably lasting from 7 to 12 hours.

The Schiff base can also be separated off from the reaction mixture of the first stage and then reacted with the reducing agent in the aforementioned manner. The reaction of the first stage is carried out in this case advantageously with the abovementioned ratio of the starting materials II and III and optionally with solvent at a temperature between 80 and 160 ⁰ O, preferably between 120 and 150 ⁰ C, with pressure or advantageously depressurized, continuously or batchwise . This embodiment can preferably be designed in such a way that the Schiff base which is formed is continuously separated off from the reaction mixture during the reaction, for example by removing it from the circuit using a suitable solvent such as an aliphatic or cycloaliphatic hydrocarbon, for example ligroin, cyclohexane; aromatic hydrocarbons - e.g. toluene. The reaction time of the first stage is expediently 6 to 12 hours. The solution of the starting material III which has been removed from the system is then expediently mixed with the reducing agent and, if appropriate, the catalyst, and the second process stage is carried out under the aforementioned reaction conditions of the one-step procedure for 6 to

• - 8th -

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12 hours through.

The novel compounds which can be prepared by the process of the invention are Pharmaceutica, especially antihypertensive and anti-inflammatory agents. In particular, the Salts of the end products I Use in the pharmaceutical field. For example, 1-IT-isobutyl-, 1-E, 1T-dimethyl- and i-NjlT-diethyl-aminomethyl-acenaphthen for peroral and intravenous administration a long-term lowering of blood pressure, have an exciting and antidepressant effect on the central nervous system, are able to reverse the eyelid paralysis caused by Serpasil in mice and increase the effect of Norepinephrine in the spinal rat. The property of these end products I is advantageous in the case of peroral and intraperitoneal Administration to have only relatively low toxicity. The values found are set out in Table I below:

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Table I.

ΙΩ CO PO

ITH-IC ₄ H ₉ ) ₂

R-CH,

Toxicity Toxicity po. Ip.

> 200

> 200 Maximum decrease in blood pressure in mm Hg after iv. Inj.

mg / kg
5 1 0.25 0.05

150

150

150 25 23 20

36 12

24

14th

Duration of action min.

> 30 5

18th

5 3 2

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The antihypertensive effect is demonstrated in the usual way urethane-anesthetized rat detected. Blood pressure is measured from the carotid artery using Statham elements. The test substances are injected intravenously via a cannula tied into the yena jugularis. The reduction the blood pressure after administration of the test substances measured in mm Hg, the duration of action is given in minutes.

In addition, the end products I and their salts are of the general formula

θ
X ^ ^ IY ,.

wherein R ₁ , R _{2 have} the aforementioned meaning and X denotes the equivalent of an acid anion, in particular the equivalent of an anion of the aforementioned inorganic or organic acids, valuable starting materials for the production of dyes, pharmaceuticals and pesticides.

The parts listed in the following examples are parts by weight. The parts by weight are related to the parts by volume like kilograms to liters.

Example 1 <. .

1-aminomethyl-acenaphthene

300 parts of methanol and 50 parts of Raney-Mekel (washed with methanol) are introduced into a stirred autoclave with a capacity of 3,000 parts by volume. The autoclave is flushed with nitrogen. 500 parts of ammonia are then added and a pressure of 50 atm is set by forcing in more hydrogen. The autoclave is then heated to 8O ⁰ C and the hydrogen pressure is increased at on 150th In the course of 2 hours, a mixture of 240 parts of I-formylacenaphthene and 60 parts of benzene is then pumped into the autoclave with stirring.

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To rinse the injection line, another 200 parts of methanol are injected. The autoclave is kept at 80 ° C. for 6 hours. The pressure drops to 130 atm over the course of 6 hours. The autoclave is allowed to cool and the pressure is released. The reaction mixture (695 parts) is first freed from methanol and water and small amounts of ammonia by fractional distillation at 20.Torr. The mixture is then fractionated at 0.5 torr on a 5-tray column. Up to a transition temperature of 155 ⁰ C 15 parts become * - 144 parts of 98.8 wt owned go 1-Aminomethyl-aeenaphthen about 0.5 Torr 155-157 ⁰ C. A follow-up at the same pressure up to a ^{transition temperature of 175 °} C. is obtained in an amount of 18 parts. The residue is viscous when cooled (70 parts). The hydrobromide of 1-aminomethyl-acenaphthene is obtained by neutralization with hydrobromic acid. It is recrystallized from ethanol and has a melting point of 254 ° C

Example 2

1-dimethylaminomethyl-acenaphthene

In a stirred vessel (250 toluene parts) with reflux condenser, 46 parts of 1-IOrmy1-acenaphthene are refluxed for 8 hours with 69 parts of 98 percent formic acid and 33 parts of 40 percent by weight aqueous dimethylamine solution. Then 120 parts of 30 percent strength by weight aqueous potassium hydroxide solution are added and the mixture becomes half. Heated to the boil for an hour. After cooling, an organic phase (47 parts) forms, which is separated off and washed with a little water. By fractionation of the mixture at 5.0 Torr, 36 parts of 1-Dimethylaminomethy1-aeenaphthen Kp at 126 to 130 ⁰ C obtained. The end product I is mixed with the same amount of ethanol and adjusted to pH 2 by adding aqueous hydrobromic acid (48 percent by weight). The salt crystallizes out. After recrystallization _; from ethanol / water (1: 1) 46 parts of hydrobromide are obtained. Fp = 236 ⁰ C.

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Example 3

i-diethylaminomethyl-acenaphthene

As described under Example 2 "In the same manner, 46 parts of 1-formyl-acenaphthen reacted with 69 parts of formic acid and 21 parts of diethylamine. The 1-Diäthylaminomethylacenaphthen proceeds 163-165 ⁰ C at 5.0 Torr are next. receive a door movement of 3 parts 43 parts pure end product I. the conversion into the hydroiodide is carried out analogously to example 2. mp = 203 ⁰ C.

Example 4

i-di-n-propylaminomethyl-ecenaphthene

Analogously to Example 2, 46 parts of 1-eormyl-acenaphthene are reacted with 69 parts of formic acid and 29 parts of di-n-propylamine. In the fractional distillation at 5.0 torr, 14 parts of end product I in the boiling range 180 to 183 ⁰ C are obtained and 21 parts of end product I 183-185 ⁰ C. The hydrobromide is prepared analogously to Example 2 from both fractions. Pp = 206 ⁰ C.

Example 5 Di-iso-propylaminomethyl-acenaphthene

Analogously to Example 2, 37 parts of 1-diisopropylaminomethylacenaphthene are prepared from 46 parts of starting material II and 50 parts of diisopropylamine. Zp ^ _{Q Torr} = 175 to 178 ⁰ C. The hydrobromide melts at 218 ⁰ C.

Example 6

1-ethylaminomethyl-acenaphthene

In a stirred vessel (250 Yolumenteile) with an attachment is provided for circulating water, 64 parts of 1-formyl-acenaphthen with 30 parts of ethylamine in the form of a 50 percent aqueous solution reacted and removed with the aid of 50 parts of cyclohexane. The so isolated Schiffsche

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Base (73 parts) -Be mixed with 3 parts of Raney-nickel and in a stirred autoclave (1500 parts by volume) at 40 to 60 ⁰ C under a hydrogen pressure of 100 atm hydrogenated. In the fractional distillation of the Gemisehs 26 parts are obtained 1-acenaphthen-Äthylaminomethyl at 5.0 Torr in the boiling range 155-162 ⁰ C.

Example 7

1 - (Piperidinyl- (F) -methyl) -acenaphthene

Analogously to Example 6, 64 parts of 1-formyl-acenaphthene with 50 parts of piperidine are initially used in a separating apparatus. Schiff's base implemented. The hydrogenation is carried out analogously to Example 6 with the aid of Raney nickel. With this compound, hydrogen uptake only takes place at 80 ° C. Di ^v e fractional distillation at 5.0 Torr supplies 39 parts i- (piperidinyl (li) methyl) -acenaphthen, bp ₅₁₈₅ to 190 ⁰ C. With wäß- engined hydrobromic acid hydrobromide is obtained, which, recrystallized from ethanol , has a melting point of over 260 ° C.

Example 8

1 - (IT »U-di-n-butylaminomethyl) acenaphthene .

1-Pormyl-acenaph.then 49 parts 35 parts Di-n-butylamiai and 69 parts formic acid (98 ^ wt.) Are heated for 8 hours under reflux (140 ⁰ C). Then the mixture with 140 parts of 20-gewichtsprözentiger, aqueous potassium hydroxide solution is heated for 1/2 hour at 110 ⁰ C and separated the organic layer formed after cooling and washed with water. The fractionation of the organic phase at 5.0 Torr provides a door travel of 24 parts up to a transition temperature of 195 ⁰ C * between 1.95 and 202 ⁰ C 47 parts obtained 1- (U, F-di-n-butylaminoniethyl) -ac .enaph.then. Residue = 6 parts. The end product I is taken up with the same amount of ethanol and neutralized with 57% strength aqueous hydroiodic acid. When the mixture is standing, the hydroiodide crystallizes from mp 115 ^Q C «

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Example 9 1- (N, K-Di-iso-butylaminomethyl) -acenaphthene

Analogously to Example 8, 48 parts of 1- (N, U-di-isobutylaminomethyl) acenaphthene are obtained from 49 parts of 1-formyläcenaphthene and 35 parts of di-isobutylamine and 69 parts of formic acid (98 percent by weight); Boiling range at 5.0 mm Hg: 190 to 200 ⁰ C. The hydroiodide is obtained analogously to Example 8 and has a I ¹ P of 157 ⁰ C.

Example 10

1- (piperidinyl- (F) -methyl) -acenaphthene

The end product I described under Example 7 can also be prepared in the following way:

49 parts of 1-l ormyl-acenaphthene are refluxed (110 ° C.) for 8 hours together with 23 parts of piperidine and 69 parts of formic acid. After working up analogously to Example 8 is obtained 37 parts of 1- (piperidinyl (K) methyl) -acenaphthen from Kp _K 142 to 147 ⁰ C and a hydrochloride of melting point> 260 ° C.

Example 11

1- (hexamethyleneimino (If) methyl) acenaphthene

Analogously to Example 10, 60 parts of 1- (hexamethyleneimino- (N) -methyl) -acen.aphthene are obtained from 49 parts of 1-formyl-acenaphthene, 28 parts of hexamethyleneimine and 69 parts of formic acid; Ep = _{0 5} 195-201 ⁰ C. The hydrobromide of 1- (hexamethyleneimino (ir) methyl) -acenaphthens melts at 228 ⁰ C (ethanol / water).

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Example 12

1 - (N-Methyl-F-butyl ~ aminomethyl) -acenaphthene

Acenaphthen-formyl-i of 49 parts, butylamine N-Methyl-N-24 parts and 69 parts of formic acid is obtained analogously to Example 40 parts of i-CH-Methyl-N-butyl-aminomethylJ-acenaphthen from Ep = 180 his 185 ⁰ G. The hydroiodide melts at 175 ° C

Example 13

1 ~ (Morpholinyl (H ") - methyl) acenaphthene

Analogously to Example 10, 1- (morpholynyl- (N) -methyl) -acenaphthene is obtained with morpholine from Pp = 84 C.

Examples 14 to 32

The end products I listed in Table 2 are obtained analogously to Example 8. The table shows the meanings of the radicals R ₁ and Rp and the corresponding characteristic data.

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Table 2

Beis-p.

End product I Ep in C / mm

Halide of the end product I with the acid

Pp in C

H, -CH ₉ -CH

136-140 / 5.0

123

15 -H

-CH

CHo-CH ^

CH ₂ -OH ₂ -OH ₂ -CH ₂ -

-CH-CH ₂ -CH ₂ -CH ₂ -CH ₂ -

154-160 / 6.0

170-176 / 5

166-170 / 0.5

180

243

236

-CH ₂ -CH-CH ₂ -CH ₂ -CH ₂ -

180-181 / 0.8

228

CH ₂ -CH ₂ -CH-CH ₂ -CH ₂ -Ch ₂ CH ₃

180-186 / 0.5

198

ν- <Χί

ti

236-240 / 5 pp = 117 0

, Ex .te te R ₂ End product I
Ep · in C / mm Halide des
Substance I with
Acid E. end
the 21
22nd -H 5, PH ₂ -CH ₂ -CH ₅ . - 129-135 / 0.5
142-150 / 0.5 HBr
HCl 204
263 23
24:, · -H:;,;: ■ ■. -CH ₂ -CH ₂ -CH ₃
¹ ^ CH _x
'«.ΡΊ-Γ' ■■ ■■" ■■! ■ ■ · ■ '■■ 175-177 / 5
162-16: 6/5 HCl
HCl 264
218 ω 25th —Η '''''''^; 3
-CH ₂ -CH ₂ -CH ₂ -O-CH ₃ 200-204 / 5 HCl 190 CD 26 ^ίΛ Λ ^ -ΐ ^ Γ OTT ÖTIP ¹ * Γ ^ ΤΧ / TLI : ₂ -CH ₃ Ί "71-ί77 / 0.5 HCl 178 Il I I
te te, w te ,.,.,; ^ ^Ξ 2 ^ ^0Η 3 27 ^;
. 28
29 '
30th -CH ₃ ^: -C-CH _x
II - ^
oW "- '
-CH ₂ -CH-CH ₂ '185-187 / 0.4
Ep = 101 ^° C
228-231 / 5
... Ep =. 117 ⁰ C HBr
HBr 219
247 31 ■ '.' '■ -CH ₃ II 3 "....- ■ 180-184 / 0.4 32 -C-CH ₉ -CH _x
Il * - - ^ "■■ 222-227 / 5 ■ '.:' V * '■' '

Ο ;; ' ⁴

Claims (2)

Claims .. Process for the preparation of i-aminomethyl-acenaphthenes the general formula R, . ^ß 2 in the R., and, R _{2 can be the} same or different -can- and \. each, a hydrogen atom ,. mean an aliphatic, araliphatic, cycloaliphatic, aromatic radical, in addition Rj also an amino group, hydroxyl group,
Alkylamino group, the radical -R ^ -SÖa-, in which E, an aliphatic or aromatic radical, '"or the radical -C-I , in which the radicals R _{A can be} identical or different and each is a hydrogen atom, a. denote aliphatic or aromatic radical, can mean, or R ^ and Rp together with the adjacent
Nitrogen atom for members of a -he'terocyclic ring
can stand, characterized in that 1-IOrmyl- "acenaphthen of the Pormel OHC II with amino compounds of the general formula R ₁ - III, wherein R ^ and R _{2 have} the aforementioned meanings, and
converts a reducing agent. ■ - 19 ■ ': ί ι ^? ; ν ■? ΐ y ν ^ i: - 309821/1236 Ac; - ■: - "'V. - 19 - α.ζ. 27 807 2. i-aminomethyl-acenaphthenes of the general formula I, in which R, and R _{2 can be the} same or different and each represent a hydrogen atom, an aliphatic, araliphatic, cycloaliphatic, aromatic radical, in addition R ^ also an amino group, hydroxy group, alkylamino group, the radical R ^ -SO ₂ -, where R ~ denotes an aliphatic or aromatic radical, or the radical -C-F, in which the radicals R. are identical or different H ^ D ΤΟ 4 can and each have a hydrogen atom, one denote, can denote, or can denote, aliphatic or aromatic radical, or R ^ and R ₂ together with the adjacent nitrogen atom can also stand for members of a heterocyclic ring. Badische 'Anilin- & Soda-Fabrik AG 309821/1236