DE624563C - Process for the preparation of carbazoles - Google Patents

Description

Process for the preparation of carbazoles From the in the reports of the German Chemical Society, Vol. 15, 1I, p. z173, described work it is known that from 2 - 2'-dioxy-i - i'-dinaphthyl when heated with chlorozincaine monia naphthylcarbazole is formed in a closed tube at 32o to 330 ° C. This creates but, as can be seen from the work-up procedure described there, in large quantities By-products, so that this mode of operation, quite apart from the difficult to treat Condensation agents for which technology cannot be considered.

It is also known (see reports of the German Chemical Society, Vol. 36, p.4i6o that 2 # 2 -Diamino-i - i'-dinaphthZTlchlorhydrat on heating 2.4o to 25o ° C in the corresponding carbazole, but this is for the production des :: - 2'-Diamino-i - i'-dinaphthyls only indicated a cumbersome operation. The formation of said diamine according to Bucherer's reaction by reaction des 2 - 2 "-Dioxyi - i'-dinaphthyls with ammonium bisulfite should not be feasible be, as from your journal for practical chemistry, 2nd part, Vol. 79, p. 117, emerges. As stated there, one obtains by the action of ammonium sulfite and ammonia 2 - 2'-Dioxy-i - i'-dinaphtliyi at temperatures up to about 160 ° C the starting material almost quantitatively back.

As has now been found, carbazoles of the benzene or naphthalene series are obtained or their N-substitution products if you have 2 - 2'-dioxy-i - i'-diaryls of these Groups with ammonia, aliphatic or aromatic primary amines at temperatures heated over 2oo °. Example i 1300 parts of 2-2'-dioxy-i-i'-dinaphthyl are in an iron shaker bomb together with 277o parts aqueous ammonia (24%) Heated for 18 hours to 26o to 265o. The reaction product is made with hydrochloric acid and caustic soda exhaustively extracted; then the dinaplithocarbazole is mixed with acetone dissolved in a yield of about 91. It can be made by distillation in vacuo be cleaned and has after your dissolving from ligroin the mp. 159 °.

Example 2 27 parts of 2 - 2'-Dioxv-i - i'-dinaphtlivl are in one iron shaker bomb with 100 parts of an aqueous solution of methylamine (32%) Treated at 26o ° for 12 hours. The reaction product is in the usual way Worked up: the residue recrystallized from alcohol melts at i48 ° C. The picrate of carbazole has a melting point of 141 °. Example 3 96 parts 2 - 2'-Dioxy-i - i'-Dinaplithyl are used together with 250 parts of n-Propylamiii 18 hours long in an iron shaker bomb?, heated to 50 °. From the reaction mixture the N-n-propyldinaphthocarbazole is obtained.

Example 92 parts of 2-9'-dioxy-i-i'-dinaphthyl are 58o parts Isobutylamine heated in an iron shaker bomb for 1½ hours at 25o °. To Removal of the excess isobutylamine in vacuo, the residue is washed with benzene added and by shaking with sodium hydroxide solution of unchanged 2 - 2'-Dioxy-i - i'-dinaphthyl exempt. The i - i'-dinaphtho-2-2'-N-isobutylcarbazole is obtained in a yield of 83%. Theory. The picrate crystallizes in red-brown Needles and melts at 116 to i18 °.

EXAMPLE 5 96 parts of 2-2'-dioxy-i-i'-dinaphthyl are used in an analogous manner with 400 parts of n-butylamine, the i - i'-dinaphtho-2 is obtained after working up - 2'-N-n-butylcarbazole in a crude yield of $ '5 ° jo. The picrat melts at i29 to 13o °. -Example 6 96 parts of 2 - 2 -Dioxy-i - i'-dinaphthyl are with 40o Divide aniline in the iron shaker bomb heated to 2So ° for 15 hours. Of the The residue is steam distilled from the excess with hydrochloric acid or water Aniline exempt; the unreacted 2-2'-dioxy-i -1'-dinaphthyl is treated by treating removed with dilute sodium hydroxide solution. The residue contains the i - i'-Dinaphtho-2-2'-N-phenylcarbazole, whose picrate melts at 169 °. (See reports of the German Chemical Society, Vol. 15, p. 2i7.5,) - Example 7 95 parts of 2-2'-Dioxy-i-i'-dinaphthyldisul- @, fonsaures Sodium is mixed with 40o parts of aqueous ammonia (24% strength) at 2o ° in an iron shaking autoclave Treated for 1S hours. The reaction mixture becomes in quantitative yield after working up the sodium dinaphthocarbazole disulfonic acid obtained.

Example S 15 parts of octohydrogenated 2-2'-dioxy-i-i'-dinaphthyl are with 40 parts of ammonia water (24%) for 9 hours in an iron autoclave on?, so 'heated. The reaction residue is worked up in the usual way Way.

r Example 9 3o parts of 2-2'-dioxy-i-i'-di.phenyl are mixed with ioo Partial aqueous ammonia (24%) heated to 260 ° for 9 hours. The residue is evaporated to dryness in vacuo, taken up with benzene and diluted with Sodium hydroxide solution shaken overnight. Remains after evaporation of the benzene pure carbazole.

Example io 27 parts 2 - 2 rDioxy-i - i'-diphenyl with a 32% aqueous methylamine solution in the iron rocking bomb for 12 hours heated to 26o °. The residue is worked up in the usual way. The end Recrystallized alcohol N-methylcarbazole melts at 86 °.

Claims (1)

PATENT CLAIM: Process for the production of carbazoles of the -Benzol- and naphthalene series, characterized in that 2-2'-dioxy-i-i'-diphenyls or -dinaphthyls with ammonia or primary aliphatic or aromatic amines brings to implementation at temperatures above 2oo °.