DE2454634A1 - AETHANOANTHRACENE - Google Patents

Description

ETHANOANTHRAZSNB

United States

United States

The invention relates to new 9,12-bridge ethanoanthracenes with a nitrogen atom in the bridging group and methods for making such compounds.

9,10-ethanoanthracenes without bridges are known and certain 9,12-bridge ethanoanthracenes have already been described (see Meek et al., J. Am. Chem, Soc, J4, 761 (1952); ibid. £ 8,5413 (1956); ibid, 82, 2566 (1960); Alder and Heimbach, Chem. Ber., 86, 1312 (1953); GB-PS No. 1,266,890). A low yield of 9,12-bridge ethanoanthrazene der formula

CHOCH ₂ CH = CK ₂

509821 / 1.Q9

is obtained by intramolecular Dlels-Ald ^ r reaction (see Heek and Dann, J. Org. Chem., 21., 963 (1955)).

The invention relates to compounds of the general Formula ·· · ■ -. -, .. · ■■

where X represents a linear chain of 3 atoms, 'which contains not much more than a central nitrogen atom, the above-' * '

. rigen atoms are carbon atoms, substituted with water- '" substance ,, or up to an oxygen atom to form 'the car—,' · '"' - • bonyl group, and v / o N with H, alkyl with up to 12 carbon atoms, Hi alkenyl, linked to the N by a saturated one s carbon atom, cycloalkyl with 3 to 9 carbon atoms ,. Cycloalkenyl, cycloalkyl-lower alkyl, phenyl-lower alkyl, -. . · Cyoloalkylniethyl having 4 to 10 carbon atoms ,. Adamantvl- ■ methyl, benzyl, <^ - furylmathyl, ^ -Thiophenylmethyl, Cycloalkenyl- -lower alkyl ~ or ß-phenylaethyl is substituted, provided that, that X has no carbon-carbon double bond ... . '. ■ -.'.-- "- ■.

The preferred X bonds are .... ■ '··. ". ··. ■

•: - - CH ₇ --NfI ⁵ - CKj - ' · "■■' ■ '■.

where R is H, alkyl with up to 12 carbon atoms (especially a Nxederalkyl), Cycloalkylmethyl with 4 to 10 carbons ■ Substance represents atoms or benzyl. . '

R and R are identical or different and can be hydrogen. -. Lower alkyl, lower perfluoroalkyl, halogen, lower alkoxy, lower alkylthio, 'lower perfluoroalkylthia', lower acyl, lower. alkylsulfonyl, lower perfluoroalkylsulfonyl, di (lower alkyl) - .. "aminosulfonyl, sulfamyl, amino, lower alkylamino xxnd. Di (never - -

509821 / 1.096 -.'..'- 'BAD ORfGiNAL

deralkyl) amino, with the gate exposure that min-

1 ?

at least one R and R is hydrogen. Preferably be-1 ρ

one R or R indicates chlorine and the remainder of R is hydrogen.

The term "down" as used herein means 1 to Carbon atoms.

Some of the compounds according to the invention, e.g. the amines, are subject to rearrangement to dihydromethanodibenzocycloheptapyrroles when heated with an acidic catalyst, the after reduction give tetrahydro derivatives, as in the ÜS application 448 686 of March 6, 1974 described .. The invention Amides or lactams can be caused by the action of bromine in a solvent such as methylene chloride Dibromodihydromethanodibenzocycloheptapyrroleones rearranged Verden. The bromine is then removed and the lactam added the above-mentioned tetrahydro derivatives reduced. Many of the latter compounds are sedatives for warm-blooded

All compounds according to the invention can be used as inhibitors free radical vinyl polymerization.

The invention therefore also relates to the use of the compounds according to the invention as inhibitors in the case of free radicals initiated vinyl polymerization.

The 9.1 ^ bridge ethenoanthracenes are numbered as follows:

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These compounds are mimicked by internal Diels-Alder reactions of the corresponding alkynyl-substituted anthracenes using the following equation (1):

X-C = CH

This process can be carried out by heating the alkynyl anthracenes, either as such or in a suitable inert solvent, preferably in an aromatic hydrocarbon at a temperature of 80 to 250 ^° C., depending on the particular atoms in the X chain and the nature of the substituents R. The reaction is run for a sufficient time to achieve cyclization, preferably 1 to 48 hours. . _:

■ I

The following reactions can be used to prepare the starting material required alkynylanthracenes are used.

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CH -NH-R-2

H CsCH

9 ~ anthraldehyde is reacted with an appropriate amine at 25 to 15O ⁰ C in an alcoholic solvent at a · Imin. The imine is then reduced with a metal hydride reducing agent such as sodium borohydride or sodium cyanoborohydride in an alcohol such as methanol, ethanol or isopropanol, which can be the same solvent that was used to form the imine, at a temperature between 0 and 100 ⁰ C.

That. secondary amine is then obtained with a propargyl halide, preferably propargyl bromide, in the presence of an inorganic base such as an aqueous solution of an alkali metal carbonate or an organic base which does not substantially react with propargyl bromide, e.g. certain hindered amines including diisopropylethylamine, at one temperature from 0 to 100 ⁰ C, preferably implemented at room temperatures.

The alkynyl-substituted anthracenes then become one Compound of formula I cyclized as described above.

According to the procedure for preparing N-containing yon Verbindlangen of formula I, wherein R ^ is H, propargylamine is reacted with a 9-anthraldehyde in alcohol at 25 to 150 ⁰ C for Imin umgesetztri ^. The imine can then be cyclized as described above and are then reduced with sodium cyanoborohydride in an alcoholic solution at 0 to 100 ⁰ C. On the other hand, the reduction can also be carried out before the cyclization.

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The above procedure provides compounds of the formula

which can then be alkylated or acylated to introduce various R substituents on the nitrogen atom. the Acylsubstuenten can then to the corresponding amine be reduced.

However, there is yet another method of converting a 9-halogen methyls, preferably Chlormethylanthrazen with RrNH ₂ in an inert solvent at room temperature to 15O ⁰ C for one substituted with a secondary amine anthracene, which is then reacted with propargyl halide, preferably the bromide, as described above.

However, other methods of preparing the various specific compounds can also be used, such as is evident from the examples in the description.

The following examples do not serve as a restriction, but only to illustrate particular compounds according to the invention according to particular embodiments of the invention.

example 1

3,5-dihydro-5,9b-above 2 above z / ej ^r isoindol-1 (2H) -one.

oToTol -> - roToTo

COCX

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A mixture of 18.85 g of 9-anthroic acid and 60 ml of thionyl chloride is heated under reflux for one hour »; The excess thionyl chloride is removed under vacuum (30 min; 9Q ° bath temperature), 50 ml of toluene then added and the mixture again concentrated. This is repeated again, after which 20.6 g of 9-anthroyl chloride are found to be very moisture-sensitive yellow solid.

A solution of 13.68 g of 9-anthroyl chloride in 30 ml of tetrahydrofuran is then added at 10 to 15 ° to a solution of 10 g of propargylamine in 60 ml of tetrahydrofuran. After stirring at room temperature for 4 hours, the solvent is removed and the residue is stirred with methylene chloride and a 5% aqueous sodium bicarbonate solution. The methylene chloride layer is dried and concentrated to give 14.54 g of the crude N-propargyl-9-anthramide as a plague body. An analysis sample (ethanol) had a melting point of 201 to 202 ⁰ C; H NMR Spectrum rci, 5-2.8 (m, 9); 3.7 (broad, 1); 5.7 (d of d, 2) and 7.7 (t, 2.5 Hz, 1).

Analysis calculated for C ₁₈ H ₁₃ NO; C 83.37; H 5.05; N 5.40 Found: C 83.50; H 5.08; N 5.29,

A mixture of 10 g of crude N-propargyl-9-anthramide and 200 ml of p-xylene is refluxed overnight. That Solvent is removed and the residue sublimed at a bath temperature of 200-210 ° (0.5 microns). Crystallization of the sublimate from 110 ml of acetonitrile gives 4.7 g 3,5 ~ dihydro-5,9b-o-benzenobenz '/ e7isoindol-1 (2H) -one with a Melting point of 264 to 265 ° C, which remains unchanged after recrystallization. Nuclear Magnetic Resonance Spectrum: T 2.3-3.3 (m, 10); 4.8

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(d, J = 6 Hz, 1) and 5.9 (d, J = 2 Hz, 2).

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Analysis calculated for C ₁₈ H ₁₃ NO: C, 83.37; H 5.05; N 5.40 Found: C 83.19; H 5.11; W 5.40.

2_-methyl ~ 3,5-dihydro-5, 9b ~ o-benzenobenz / eyisoindo.l-1 (2H) -one

HCH ₃

After the process method given in Example 1 is obtained

one using N-methylpropargylamine instead of

Propargylamine:

N-methyl-N-propargyl ~ 9-anthramide as an oil; H NMR spectrum:

Τ 1.7-2.9 (m, 9); 5.4 (d, 2.5 Hz, 1.3); -6.4 (d, 2.5 Hz, 0.7); 6.7 (s, 0.9); 7.4 (s, 2.1); 7.7 (t, 2.5 Hz, 0.7) and 8.0 (t, 0.3). The spectrum shows the presence of two rotamers.

2-methyl ~ 3,5-dihydro-5,9b-o-benzenobenz / e_ / isoindol-1 (2H) -one, Br 250-255 ⁰ C; Nuclear Magnetic Resonance Spectrum: T 2.3-3.3 (m, 9); 4.8 (d,

J = 6 Hz, 1); 5.9 (d, J = 2 Hz, 2) and 6.9 (s, 3).

Analysis calculated for C ₁₉ H ₁₅ NO: C, 83.49; H 5.53; N 5.13 Found: C 83.84; H 5.66j N 5.10.

example $

3 , 5-dihydro-5,9b-o-benzenobenz / e7isoindole

II ₂ CaCH

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A mixture of 16.7 g of 9-anthraldehyde, 5 g of propargylamine and 100 ml of ethanol is heated under reflux for one hour. The solvent is removed and the residue crystallized from 100 ml of acetonitrile, after which 16.1 g (82%) of N-propargyl-9-anthrazenmethylenimin having a melting point 143-144 ⁰ C is obtained; Nuclear Magnetic Resonance Spectrum: T- 0.2 (t, 2 Hz, 1); 1.7-3.0 (m, 9); 5.1 (t, 2Hz, 2) and 7.3 (t, 2Hz, 1).

Analysis calculated for C ₁₈ H ₁₃ N: C, 88.86; H 5.39; N 5.76 Found: C 88.83; H 5.56; N 5.87.

A mixture of 19.4 g of crude N-propargyl-9-anthrazenmethyleneimine and 200 ml of ρ-xylene is heated under reflux for 3 hours. On cooling, 14.6 g of 3,5-dihydro-5,9b-o-benzenobenz / e / isoindole with a melting point of 212 to 214 ° C. precipitate. A further 1.4 g of the product are obtained when the solvent is removed from the mother liquor and the residue is crystallized from 50 ml of acetonitrile; Nuclear Magnetic Resonance Spectrum: X 1.1 (m, 1) i 2.5-3.5 (m, 9); 4.8 (d, J = 6 Hz, 1) and 5.4 (t, J = 2 Hz, 2).

Analysis calculated for found:

C 88.86; H 5.39; N 5.76 -C 89.10; H 5.58; N 5.66.

3,5-dihydro-5,9b-o-benzenobenz / eyisoindol can also be used directly by heating 9-anthraldehyde with propargylamine in p-xylene can be obtained.

Example, 4

1 »2,3,5-tetrahydro-5,9b-o-benzenobenz / e / isoindole

CH ₂

/ ■

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To a slurry of 10.19 g of 3,5-dihydro-5,9b-o-benzenobenz / e / -isoindole in 50 ml of methanol and 10 ml of acetic acid, 4.70 g of sodium cyanoborohydride are slowly added with cooling. The mixture is then stirred overnight at room temperature, the excess hydride is destroyed with concentrated hydrochloric acid (ice bath) and the mixture is made alkaline and extracted with the methylene chloride. After removing the solvent, 10.49 g of 1,2,3,5-tetrahydrα-5,9b-benzenobenz / e / isoindole are obtained from the dry extract as an oil which slowly solidifies; Nuclear Magnetic Resonance Spectrum: τ 2.6-3.7 (m, 9); 4.9 (d, 6 Hz, 1); 6.0 (s, 2); 6.5 (d, 2 Hz, 2) and 7.5 (s, 1). The hydrochloride melts at 273 ° C. (decomp.) After crystallization from isopropyl alcohol.

Example, 5 ..

2-methyl-1,2,3,5-tetrahydro- 5,9b-o -benzenobenz / e / isoindole

A mixture of 8.19 g of 3,5-dihydro-5,9b-o-benzenobenzene / isoindole, 25 ml of acetic acid and 25 ml of an aqueous formaldehyde solution is heated under reflux for 3 hours. Concentrated hydrochloric acid (10 ml) is then added and the volatiles removed. The residue is stirred with aqueous sodium hydroxide solution and methylene chloride. After removing the solvent from the dried methylene chloride extract and crystallizing the residue from acetonitrile, two batches of 5.04 g (58%) of 2-methyl 1,2,3,5 ~ tetrahydro ~ 5,9b-o-benzenobenz / e / isoindole with a melting point of 196 to 197 ⁰ C; Nuclear Magnetic Resonance Spectrum: T 2.4-3.1 (m, 8); 3.3 (d of t, J = 6/2 Hz, 1); 4.8 (d, 6 Hz, 1); 6.1 (s, 2); 6.6 (d, 2 Hz, 2) and 7.3 (s, 3).

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Analysis calculated for found:

C 87.99; H 6.61; N 5.40 C 88.05; H 6.91; N 5.32.

The N-methyl compound of the present example can also are obtained by reacting 1,2,3,5-tetrahydro-5,9bo-benzenobenz / e / isoindole with formaldehyde and formic acid under similar reaction conditions.

Example 6

2 ~ Cyclopentylmethyl- * 1,2,5,5-tetrahydro-5 , 9b-o-benzene o benz / eZ -isoindole

CHO

CH ₂ NHCH;

-Q

CH ₂ K-CrI ₂
CII ₂ C = CH

CK ₂

N-CK ₂

5 0 9 8 21/10 9 6

A mixture of 43.5 g of 9-anthraldehyde, 20.97 g of cyclapentylmethylamine and 150 ml of ethanol is refluxed for 1.5 hours. The hot N-cyclopentylmethyl-9-ahthrazenmethyleneimine solution is then cooled to 60.degree. C. and 8.2 g of sodium borohydride are added in small amounts with stirring while the temperature is maintained at 55 to 60.degree. The mixture is then stirred for an additional 1.5 hours, concentrated hydrochloric acid (35 ml) added with cooling and stirring continued for half an hour. The mixture is then made alkaline and extracted with methylene chloride. Removal of the solvent from the dried extract gives 59.1 g of N-cyclopentylmethyl-9-anthracenemethylamine as an oil. NMR spectrum: r 1.8-3.1 (m, 9); 5.6 (s, 2); 7.5 (d, 7 Hz, 2) and 7.8-9.3 (m, 10).

A mixture of 63.5 g of N-cyclopentylmethyl-g-anthracene methylamine, 50 g propargyl bromide, 200 ml methylene chloride and 200 ml of 10 ^ aqueous potassium carbonate solution becomes violent stirred under nitrogen for two hours. The layers are separated and the aqueous layer once with methylene chloride extracted. Removal of the solvent from the dried extract gives 63.5 g of N-cyclopentylmethyl-N-propargyl-9-anthracenemethylamine as oil; Nuclear Magnetic Resonance Spectrum: r 2.3-3.0 (m, 9); 5.5 (s, 2); 6.8 (d, 2.5 Hz, 2); 7.5 (m, 2) 7.7 (t, 2.5 Hz, 1) and 7.5-9.2 (m, 9). This product is cyclized by refluxing in 200 ml of toluene for 1.25 hours.

Removal of the solvent and crystallization of the residue from 150 ml of isopropyl alcohol gives 44.4 g 2-Cyclopentylmethyl-1,2,3,5-tetrahydro-5,9b-o-benzenobenz / e / -isoindole, which is identical to the sample prepared by acylating from due to its infrared and NMR spectrum 1,2,3,5-Tetrahydro-5,9b-o-benzenobenz / e / isoindole with cyclopentanecarbonyl chloride and subsequent reduction.

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Using the same procedure, but replacing Cyclopentylmethylamine substituted by the corresponding amine and 9-anthraldehyde are the following 2-substituted 1 ^^, S-Tetrahydro - ^^ b-o-benzenobenz / e / isoindole obtained:

2-cyclopropyl-1 ^^, S-

dol, melting point 109 to 110 ° C;

Analysis calculated for C ₂₁ H ₁₉ N: C, 88.38; H 6.71; N 4.91 Found: C 88.21; H 6.68; N 5.06.

2-cyclohexyl-1,2,3,5-

dol, melting point 152 to 154 ⁰ C;

Analysis calculated for C ₂ → H ₂₅ N: C, 88.03; H 7.70; N 4.28 Found: C 87.82; H 7.77; N 4.35.

2-benzyl-1,2,3,5-tetrahydro-5,9b-o-benzsnobenz / e / -isoindole, identical by NMR spectrum comparison with a sample that by benzoylation of 1,2,3,5-tetrahydro-5,9b-o-benzeno- ' benz / ei / isoindole and subsequent reduction were obtained is.

8-chloro-2-cyclohexylmethyl-1,2,3,5-tetrahydro-5,9b-o-benzenobenz / e / isoindole; Melting point 144 to 146 ° C;

Analysis calculated for C ₂₅ H ₂₆ ClNt C 79.87; H 6.97; N 3.73 Found: C 79.74; H 7.09; N 3.66.

Example 7

2-Cvclopropylmethyl-i, 2,3 »5-tetrahydro-5, 9b-o-benzenesabove z / e7-isoindole

CH ₂

^ CH ₂ NCO-CH I

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To a pulp of 3 »75 g of 1,2,3,5-tetrahydro-5,9b ~ o-benzenobenz / e / isoindole and 3 g of magnesium oxide in 20 ml of anhydrous tetrahydrofuran slowly becomes a solution of 2.4 g of cyclopropanecarbonyl chloride added in 5 ml of tetrahydrofuran. After stirring at room temperature for 5 hours, the mixture becomes filtered and the filtrate concentrated to dryness. The residue is taken up in methylene chloride with sodium bicarbonate solution washed and dried. After removing the solvent, 4.07 g of crude 2-cyclopropylcarbonyl-1,2,3,5-tetrahydro-5,9b-o-benzenobenz / e7isoindole are obtained, which is used in the next stage without further purification. One crystallized twice from isopropyl alcohol Sample had a melting point of 171 to 173 ° C.

Analysis calculated for C ₂₂ H ₁ QNO: C, 84.31; H 6.11; N, 4.47 Found: C, 84.41; H 6.31; N 4.88.

A mixture of 9.87 g of crude 2-cyclopropylcarbonyl-i, 2,3,5-tetrahydro-5,9b-o-benzenobenz / e / isoindole, 4.83 g of lithium aluminum hydride and 100 ml of tetrahydrofuran is heated under reflux for 2 hours. The cooled mixture is treated successively with 4.8 ml of water, 4.8 ml of 1.5% sodium hydroxide solution and 14.4 ml of water. The concentration of the filtered mixture yields 9 »29 g crude 2-cyclopropylmethyl-1,2,3,5-tetrahydro-5,9b-o-benzenobenz / e / isoindole which melts after a single crystallization from isopropyl alcohol at 109-110 ⁰ C. . Nuclear Magnetic Resonance Spectrum: Γ 2.5-3.5 (m, 9); 4.8 (d, 6 Hz, 1); 6.1 (s, 2); 6.5 (d, 2 Hz, 2); 7.3 (d, 6 Hz, 2) and 8.7-9.8 (m, 5).

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Analysis calculated for C ₂₂ H ₂₁ N: C, 88.25; H 7.07; M 4.63 '. Found: C, 87.87; H 7.35; N 4.70. "

If the procedure is as in Example 7, however, cyclopropanecarbonyl chloride is replaced substituted by the appropriate. · Carbonyl chloride, one obtains the following- / 2 ~ substituted i, 2,3,5-tetrahydro-5, gb-o-benzenobenz / e / isoindola. -..All these Compounds have an NMR spectrum, which

characteristic of 1,2,3,5-tetrahydro- ^ b-o-benzenobehz / e / isoindole is: . . . -.

■ T. 2.6-5 ^ 2.Cm, 8); 3.4-3.5 Cd / t, 6.2 Hz, 1); "4.6-5.0 (d, 6 Hz, 1), 6.0-6.3 (s, _- 2) and _: 6.6-6.8 (d, 2 Hz, 2) with smaller variations in the chemical rearrangement - '' .._ ■

. ^ e after the 2-substituents. Additional signals from each -2 * substituent are listed separately for each connection.

. - 2-Xtliyl-1 -, 2,3,5-tetrahydro-5, .Sb-o-benzenobenz / e / isoindole; _ "Hm-Spektruai: .ir 7.3 (q, 7 Hz, 2); 8.7 (t, 7 Hz,. 3).

'2 ~ is'obutyl-1,2,3,5-tetrahydro-5, 9b-o-benzenobenz / e_ / isoindole; MMR spectrum: T. 7.6 (d, 7 Hz, 2); 7.7-8.5 (m, 1); 9.0 (d, 7 Hz, 6) .-. ■ - ■ '■■■ ".. ..

2 ~ neopentyl-1,2,3,5-tetrahydro-5, Sb-o-benzenobenz / e / isoindole; . HMR Specification: r 7.5 (s, 2); 9.0 (s, 9).

2-Cyciobutylmethyl-1,2,3,5-tetrahydro-5, 9b-o-benzenobenz / e7-isoindole; 'UMR-spectrum' V ^7: 1 to 8.5 (m, 9) '·'.

2-Cyclopentylmethyl-1,2,3,5-tetrahydro ^, 9b-o-benzenobenz / e7 ~ isoindole, melting point 110 to 111 ⁰ C; NI4R - Spectrum: - T "^; 7.3-9.0 (m, 1-1)..

Analysis calculated for C ₂ → H ₂₅ N: C, 88.03; H 7.70; "N-4.23

found: ■ C 87.68; H 7.75; N, 4.43. *

5-methyl ~ 2-cyclohexylmethyl-1 ^, SjS-y ^ benz / e7isoindole: M'IR spectrum: T 3.9 (t, 2 Hz, 1) (proton

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at C-4; Response missing at 4.6-5.0); 7.6 (d, 6 Hz, 2); 7.9 (s, 3); 8.0-9.5 (m, 11).

2- (2-cyclohexylethyl) -1,2,3,5-tetrahydro -5,9b-o.-benzenobenz- / e / isoindole; NMR Spectrum: r 7.1-9.5 (m, 15). .

2- (Δ-cyclohexenylmethyl) -1, 2,3,5-tetrahydro-5> 9b-o-benzene-benz / e.7isoindole; Nuclear Magnetic Resonance Spectrum: T 4.3 (m, 2); 7.5-9.0 (m, 9)

2-cycloheptylinethyl-1,2,3,5-tetrahydro -5,9b-OT-benzenobenz / e / -isoindole; Nuclear Magnetic Resonance Spectrum: r 7.5-9.2 (m, 15).

2-benzyl-1,2,3,5-tetrahydro-5,9b-o-benzenobenz / e / isoindole; NMR spectrum: V 2.4-3.0 (m, 5); 6.3 (s, 2).

2- (1-adamantylraethyl) -1,2,3,5-tetrahydro-5,9b-o-benzenobenz- / e / isoindole; ΝΓ'Η - spectrum: T 7.6 (s, 2); 7.5-8.5 '(m, 15)

2- (2-phenylethyl) -1,2,3,5-tetrahydro-5,9b-o-benzenobenz / e / -isoindole; NMR spectrum; T 2.6-3.1 (m, 5); 7.0 (s, 4).

Example_8

2-Cyclohexylmethyl-1,2,3,5-tetrahydro-5,9b-o-benzenobenz / e7- isoindole

CHp

NCO

-O

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If you work as described in Example 7 and use cyclohexanecarbonyl chloride instead of cyclopropanecarbonylochloride, the following connections are obtained:

S-Cyclohexanecarbonyl-I, 2,3,5-tetrahydro-5,9b-o-benzeneQbenz- / eyisoindole, Melting point 215 to 217 ° C.

Analysis calculated for C ₂₅ H ₂₅ NO: C 84.47, H 7.09; N 3.94 Found: C 84.36; H 7.05; N 4.00.

2H-cyclohexylmethyl-1,2,3,5-tetrahydro-5, 9b-o-benzenobenz / e / ~ isoindole, melting point 157 to 158 ° C. 'NMR spectrum r 2.5-3r5 (m, 9); 4.9 (d, 2 Hz, 2); 7.5 (d, 6 Hz, 2) and 7.7-9> 5 (δι, 11). . ·

Analysis calculated for C ₂₅ H ₂₇ N: C, 87.93; H 7.97; N, 4.10 Found: C, 87.80; H 7.66; N 4.29.

2-chloro-9-anthraldehyde and 2,6 ~ dimethoxy-9-anthraldehyde can as described in the literature as starting materials according to the general procedure of Examples 3 and 6 used to substitute the appropriate 9. »12-bridge ethenoanthracene (I) as reaction products obtain.

The following 9-anthroic acids can be used as described in the literature described as starting products according to the. general procedure of Examples 1 and 2 are used, to the corresponding substituted 9,12-bridge ethenoanthracenes (I) to obtain as reaction products:

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i-chloro-9-anthroin-, 2-chloro-9-anthroin ~, 1,5-dichloro-9-anthroin-, 2-methyl-9-anthroin-, 3-chloro-9-anthroin-, 1,4-dichloro-9-anthroin-, 2,5-dichloro-9-anthroic, 4,5-dichloro-9-anthroic acid. .

The compounds according to the invention are useful as polymerization inhibitors for the free radical polymerization of vinyl ¹ compounds. This application is demonstrated in relation to the inhibition of the polymerization of acrylonitrile.

Example. A.

In a Carius tube, 0.5 ml of distilled acrylonitrile, 2 ml of toluene, 20 mg of azobis (isobutyronitrile) initiator and 70 mg of 2-methyl-3,5-dihydro-5,9b-o-benzenobenz / e / isoindol-1 (2H) -one (Example 2) introduced. The tube is degassed, sealed under vacuum and shaken at room temperature overnight. No polyacrylonitrile is formed. In a comparative experiment in which the compound of Example 2 is omitted, Solid polyacrylonitrile separates from the solution.

Similarly, when the following compound is used as an inhibitor, there will be no polymerization of acrylonitrile instead of:

2-methyl-1,2,3,5-tetrahydro-5,9b-o -benzenobenz / e / -isoindole (Example 5). .

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Claims (1)

Claims . 1 * compound of the formula 1 'Z where R and P. are identical or different and are hydrogen.,. Alkyl having 1 to 12 carbon atoms, lower perfluoroalkyl, halogen,; iilower alkoxy, lower alkyl thio, lower perfluoroalkyl- "■ thio, lower acyl, lower alkylsulfonyl, lower perfluoroalkyl sulfonyl, di (lower alkyl) aminosulfonyl, sulfamyl, amino, lower Aikylamino and di (lower alkyl) amino mean, X means a linear chain of j5 represents atoms which cannot contain more than one central nitrogen atom, the remaining atoms being carbon atqm.e which are substituted with hydrogen, or up to. an 'oxygen atom to form a carbonyl'. group, where N is substituted with H, - lower alkyl, lower alkenyl, connected to the N by a saturated carbon atom, cycloalkyl with 3 to 9 carbon atoms, cycloalkylmethyl with 4 to 10 carbon atoms, adaniantylmethyl, pe-. "Furylmathyl, OL -Thiophenylmethyl * Cycloalkenyl, 'Cycloalkyl- ■ /. Lower alkyl, · Cycloalkenyl-lower alkyl, phenyl-lower alkyl or β-phenylethyl, provided that X has no carbon-carbon double bond. 5 0 9 8 21/10 9 6 2. A compound according to claim 1, characterized by the formula where X -CH ₂ - M? - CH ₂ - means and V? Is hydrogen, alkyl of up to 12 carbon atoms, cycloalkylmethyl of 4 to 10 carbon atoms or benzyl. 3. Connection according to claim 2, characterized 1 2. ze I et η that R and R are each hydrogen. 4. A compound according to claim 2, characterized in-ζ e i c h-n e. t,. that R- * cycloalkylmethyl having 4 to 10 carbon atoms means. 5. A compound according to claim 2, characterized in that that R is cyclobutylmethyl. 6. A compound according to claim 2, characterized in that it is 25 calibrates.,. that R is cyclopentylmethyl. 7 # connection according to claim 2, characterized 5
indicates that R is cyclohexylmethyl. 509821/1096 8, connection- according to claim 2, characterized in that g e k e n, n, - ■■ \ -. ■ c · ζe £ c h n e t that R ^ cycloheptylmethyl. means.. · 9- connection according to claim 2, that you rchgekenn- ' Ssee that R- * means lower alkyl- '. ·. 10, connection according to claim 3? durchgeke n. n- ζ ei c h. η et that R ^{D is} cyclopentylethyl. H. A compound as claimed in claim 2, characterized in that it is indicated t, · that R- * means hydrogen. ·· 12ί Process for the preparation of the compound of formula ' i 2 · '''' - "■"'"' R and R. are identical or different, and are hydrogen, · Alkyls containing up to 12 carbon atoms, lower perfluoroalkyl, Halogen, lower alkoxy, lower alkylthio, lower perfluoroalkyl thio, lower acyl, lower alkylsulphonyl, lower perfluoroalkylsulphonyl, Di (lower alkyl) aminosulfonyl, sulfamyl, amino, lower Alkylamino and di (lower alkyl) amino mean, X means a linear chain of 3 atoms which do not contain: more than one; .central nitrogen atom contains kartn. ^ where the. remaining *! Atom Kohleri- ^ atom are ,, dia are substituted with hydrogen, or up to an oxygen atom to form a carbonyl group, ■ wherein N is substituted with H, lower alkyl, · lower alkenyl, Connected to the H through a saturated carbon atom, cycloalkyl having 3 to . 9 carbon atoms, cycloalkylmethyl with 4 to 10 carbon atoms, adamantylmethyl, C ~ furylmethyl _y c <r- 'Thlophenylmethy ^ · cycloalkenyl, cycloalkyl-lower alkyl / ·. '... "- Cycloalkenyl-lower alkyl, phenyl-lower alkyl. Or ß-Phenyläthyi, provided that X has no carbon-carbon double bond, according to one of claims 1-11,. -; ■■■ 509821/1096 characterized by the fact that there are connections of the formula '..' · ": ' A ■ ρ ■ ' wotiai H and R have the above meaning "* in' known ways subjected to an internal Diels-Alder reaction * 13. Process according to claim 12, characterized in that the process is carried out in a suitable solvent at approximately 80-250 ^° C. ' 14 * Method according to claim 12 or 13 ». characterized, that one als.inertes solvent aromatic hydrocarbon used 15. The method according to claim 12-14, thereby geken n-draws that one takes about 1 to 48 hours • heats up. '·. · ·. 16. Versrandimg a compound according to claim. 1 to 11 to. Inhibition of the> .f raienv radical polymerization of vinyl compounds-; ■ ■ '· ■ ■ .'.- ■'. 509821/1096