US3541091A - Process for producing imidochloride containing compounds by two stage chlorination of secondary amines - Google Patents

Process for producing imidochloride containing compounds by two stage chlorination of secondary amines Download PDF

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US3541091A
US3541091A US694094A US3541091DA US3541091A US 3541091 A US3541091 A US 3541091A US 694094 A US694094 A US 694094A US 3541091D A US3541091D A US 3541091DA US 3541091 A US3541091 A US 3541091A
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imidochloride
chlorination
percent
chlorine
temperature
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US694094A
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Wilfried Zecher
Horst Tarnow
Hans Holtschmidt
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Bayer AG
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Bayer AG
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
    • C07D239/46—Two or more oxygen, sulphur or nitrogen atoms
    • C07D239/48—Two nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
    • C07D241/36—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems
    • C07D241/38—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems with only hydrogen or carbon atoms directly attached to the ring nitrogen atoms
    • C07D241/40—Benzopyrazines
    • C07D241/44—Benzopyrazines with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to carbon atoms of the hetero ring

Definitions

  • Chlorination of acylamines and also of tertiary amines is known and results in compounds the common characteristics of which is the imidochloride grouping (Angewandte Chemie, 74, 848 (1962)).
  • R is alkyl having 2 to 6 carbon atoms, aryl (preferably monoor dinuclear), aralkyl (preferably monoor dinuclear with an alkyl group having 1 to 6 carbon atoms) or a 5- to 6-membered heterocyclic radical, having from 1 to 3 nitrogen atoms as an only hetero atom, such heterocyclic ring possibly containing a fused 4- to 6-membered carbocyclic ring system.
  • radicals may be substituted with one or more of the same or different halogen, cyano, alkoxy with 1 to 6 carbon atoms, aroxy (preferably monoor di- 3,541,091 Patented Nov. 17, 1970
  • R is alkyl having 1 to 6 carbon atoms, aryl (preferably monoor dinuclear), aralkyl (preferably monoor dinuclear with an alkyl group having 1 to 6 carbon atoms) or a 5- to 6-membered heterocyclic radical, having from 1 to 3 nitrogen atoms as an only heteroatom, such heterocyclic ring possibly containing a fused 4- to 6-membered carbocyclic ring system,
  • R may also stand for halogen, cyano, chyorocarbonyl, hydro carbonyl, alkoxycarbonyl (preferably with 1 to 6 carbon atoms) and alkylamino (alkyl having preferably 1 to 6 carbon atoms),
  • R is hydrogen or halogen, preferably fluorine, chlorine or bromine,
  • R is defined as R but containing additional chlorine atoms introduced during the reaction.
  • the total number of chlorine atoms ranges from a complete replacement of all reactable hydrogen atoms to a partial replacement depending on the reaction conditions and the product desired,
  • R is defined as R respectively but containing additional chlorine atoms introduced during the reaction.
  • the total number of chlorine atoms ranges from a complete replacement of all reactable hydrogen atoms to a partial replacement depending on the reaction conditions and the product desired,
  • R may also be linked to R via one or more, same or different nitrogen, oxygen, sulphur, methine or methyl ene radicals to form a 5- or 6-membered ring. Normally from 1 to 3 such heterocyclic atoms are preferred. In such a case,
  • R and R are defined as R and R when so connected but containing additional chlorine atoms ranging from complete replacement of the reactable hydrogen atoms to a partial replacement again depending on the reaction conditions and the desired product.
  • substituted and unsubstituted alkyl radicals with a definition of R to R above are the following:
  • Aryl radicals are, for example:
  • Preferred aralkyl radicals are:
  • Preferred heterocyclic radicals are:
  • Examples of compounds in which R and R are linked via nitrogen, oxygen, sulphur, methine or methylene groups to form a 5- or 6- membered ring are preferably:
  • Piperazine 2-methylpiperazine, 2-cyano-5-methylpiperazine, morpholine, thiomorpholine, pyrrolidine, piperidine, tetrahydroquinoline, 5-methoxy-7-cyano-8-chlorotetrahydroquinoline, tetrahydroisoquinoline, 5,7-dichlorotetrahydroisoquinoline, tetrahydroquinoxaline, 2-, 3- or 4- methylpiperidine, 2,4-dimethylpiperidine, Z-methyltetrahydroquinoline.
  • reaction is all the more surprising as secondary amines which carry a methyl group as second substituent, for example N-methylaniline, are converted by the chlorination under the condition described above into chlorinated carbodiimides.
  • the secondary amines employed as starting compounds are obtainable by methods known from the literature.
  • the process may be explained by the example of the reaction of N-ethylaniline, in which a completely hydrogen-free compound is formed in the presence of a catalyst.
  • the conditions of chlorination are to be chosen in such a way that initially, at lower temperatures of about 20 to about +60 C., all easily exchangeable hydrogen atoms are substituted by chlorine, optionally under exposure to ultra-violet rays or in other words until at the recited temperature range no further chlorine is consumed.
  • the temperature is then raised, depending on the degree of chlorination desired, to about 70 to about 250 C. to produce the desired formation of the group are valuable products for the preparation of pest control agents, herbicides, dyestuffs, pharmaceutical agents and synthetic resins.
  • pentachlorophenyl-trichloromethyl-imidochloride is an effective acaricidal agent.
  • EXAMPLE 1 Hydrogen chloride is passed into a solution of 121 g. N-ethylaniline in 250 cc. chloroform until saturation is achieved. The product is then chlorinated at about 60 C. under ultra-violet light, for about 5 hours. Then the temperature is raised for C. per hour from 60 up to 200 C. As soon as no appreciable evolution of hydrogen chloride can be detected, the temperature is allowed to decrease to about 12 C., 2 g. of iron-III-chloride are added and the chlorination is continued, whilst the temperature is again raised for 20 C. per hour up to 200 C. Chlorine is passed in at this temperature for about 8 hours and the mixture is then subjected to fractional distillation under vacuum.
  • the imidochloride distils over at -170 C. and at 0.15 mm. Hg and solidifies in the receiver to pale yellowish polyhedra of M.P. 129-130 C.
  • the yield of N pentachlorophenyl-trichloromethyl-imidochloride amounts to 360 g.
  • EXAMPLE 2 158 grams of N-ethylaniline hydrochloride are chlorinated in 250 cc. chloroform under ultra-Violet light for about 8 hours at 40 C. The temperature is then increased for 5 C. per hour from 40 C. up to 90 C. and the chlorination completed at this temperature in about 8 hours. The reaction mixture is distilled under vacuum. Heptachloro-N-phenyl-methyl-imidochloride of B.P. C./1 mm. Hg is obtained.
  • EXAMPLE 3 183 parts by Weight of N-benzylaniline are dissolved in 200 parts by weight of chloroform and converted into the hydrochloride by introduction of hydrogen chloride, followed by vigorous chlorination within about 4 hours at temperatures between 20 and 60 C. The chloroform is slowly removed by the chlorine current during this time and the temperature is then raised by 10 C. per hour to 200-220 C. After addition of 3% by weight of FeCl, chlorination is continued at 200 C. The resulting crude imidochloride is purified by recrystallisation from benzine with the addition of 20% by volume of xylene. The compound of the formula 01 C1 C1 G1 I I I I l G1 I C1 All C1 C1 is obtained in a yield of 90%. M.P. 273-275 C.
  • EXAMPLE 4 298 parts by weight of N-isobutylaniline are dissolved in 200 parts by weight of chloroform and converted into the hydrochloride by passing in hydrogen chloride. The subsequent chlorination is carried out as in Example 3 and purification by recrystallisation from benzine. The compound of the formula is obtained in a yield of 87% of the theoretical. M.P. 135l36 C.
  • Chlorine is passed into the suspension of the hydrochloride and the temperature raised within about ten hours from 50 to 200 C. Chlorination is now carried out for six hours at 200 C., the temperature is allowed to fall to 120 C. for the addition of 3 g. of iron-III- chloride and then within about four hours raised again to 200 C. The chlorination is continued at that temperature for about a further 6 hours, in order to complete the exchange of all hydrogen-atoms for chlorine.
  • the reaction mixture is taken up in hot light benzine, the solution treated with activated carbon, and insoluble parts are filtered off from the solution.
  • the N pentachlorophenyl pentachloroethyl imidochloride crystallises out in the form of pale yellow polyhedra of M.P. 132-134 C. After recrystallisation from light benzine the M.P. is 135136 C.
  • EXAMPLE 7 170 grams of piperidine in 250 cc. chloroform are converted into the hydrochloride by introduction of hydrogen chloride, followed by chlorination for about 16 hours at 45 C., under ultra-violet light. The temperature is then gradually raised for 10 C. per hour up to 200 C. and chlorination continued at 200 C. for about 7 hours.
  • Trichloropyridine of B.P. 95 C./l2 mm. Hg and tetrachloropyridine of B.P. ll0-125 C./12 mm. Hg are obtained by distillation.
  • the pentachloro-quinoline from 1,2,3,4-tetrahydro-quinoline; the trichloro-pyrazine from piperazine.
  • EXAMPLE 8 193 parts by weight of 2,4-dichloro-6-ethylamino- 1,3,5- triazine are dissolved in 400 parts by weight of chloroform and chlorinated initially at 020 C. After about one hour, the product is exposed to ultra-violet rays and the temperature increased to 60 C. within about 5 hours, whereby the chloroform is gradually driven oil by the flow of chlorine. The chlorination is continued by raising the temperature to about 10 C. per hour up to 200 C.
  • the product crystallises upon cooling and can be purified, either by distillation or recrystallisation from benzine.
  • the compound of the formula is obtained in a yield of of the theoretical. B.P. 153-160 C./0.3 mm. Hg. M.P., 119-121 C.
  • EXAMPLE 9 201.5 parts by weight of 2-chloro-4,6-bis-ethylamino- 1,3,5-triazine are dissolved in 400 parts by weight of chloroform and chlorinated as described in Example 8. After removal of the chloroform, 500 parts by weight of trichlorobenzene are added. After termination of the chlorination at 200 C., the trichlorobenzene is distilled off under vacuum and the residue recrystallised from benzine.
  • chloroethyl-imidochloride)-triazine from chloro-ethylamino-propylamino-triazine.
  • N-(2- chlorocarbonyl-dichlorophenyl) trichloromethyl imidochloride is obtained by distillation as a yellow liquid.
  • a process for the production of chlorine-containing organic nitrogen compounds containing from 1 to 4 imidochloride groupings having the formula which comprises reacting a secondary amine having the formula:
  • n is a whole number from 1 to 4,
  • R when taken alone is a member selected from the group consisting of alkyl having 2 to 6 carbon atoms, mono or dinuclear aryl, mono or dinuclear aralkyl, the alkyl group having from 1 to 6 carbon atoms, a 5 or 6 membered heterocyclic radical having from 1 to 3 nitrogen atoms as the only hetero atoms and a 5 or 6 membered heterocyclic radical having 1 to 3 nitrogen atoms as the only hetero atoms containing a fused 4 to 6 membered carbocyclic ring, said members being optionally substituted by halogen, cyano, alkoxy having from 1 to 6 carbon atoms, mono or dinuclear aroxy chlorocarbonyl, sulfur chloride, alkyl having from 1 to 6 carbon atoms, mono or dinuclear aryl, or amino having two radicals attached to the nitrogen, said radicals when taken along being alkyl having from 1 to 6 carbon atoms or mono or dinuclear aryl and said radicals when
  • R when taken alone stands for alkyl having from 1 to R and R when taken together are a 5 or 6 membered heterocyclic ring wherein R and R are linked together with methine or methylene groups and wherein such groups may additionally contain up to 2 nitrogen atoms, an oxygen atom or a sulfur atom with the proviso that the heterocyclic atoms are not adjacent one another on the ring, and
  • R stands for hydrogen or halogen, with chlorine at a temperature between about 20 and +60 C. until all easily exchangeable hydrogen atoms are replaced by chlorine, continuing the chlorination at a temperature between about 70 to 250 C. and isolating the resulting imidochlorides.
  • the final phase of the chlorination is carried out in the presence of halogen-yielding agents selected from the group consisting of A1C1 AlBr FeCl SnCl BF TiCl 3.
  • R and R are taken together and are a ring selected from the group consisting of piperazine, morpholine, thiomopholine, pyrrolidine, piperidine, tetrahydroquinoline, tetarhydroisoquinoline and tetrahydroquinoxaline.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Pyrrole Compounds (AREA)
US694094A 1964-12-21 1967-12-28 Process for producing imidochloride containing compounds by two stage chlorination of secondary amines Expired - Lifetime US3541091A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DEF44766A DE1222918B (de) 1964-12-21 1964-12-21 Verfahren zur Herstellung chlorhaltiger organischer Stickstoffverbindungen, welche die Imidchloridgruppierungí¬N = CCl - ein- oder mehrmals enthalten

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US (1) US3541091A (de)
AT (1) AT262250B (de)
BE (1) BE674020A (de)
CH (1) CH471085A (de)
DE (1) DE1222918B (de)
FR (1) FR1477466A (de)
GB (1) GB1124078A (de)
IL (1) IL24490A (de)
NL (1) NL6516622A (de)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4246200A (en) * 1978-06-08 1981-01-20 Agence Nationale De Valorisation De La Recherche (Anvar) Perfluoro intermediates and processes for their preparation

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4246200A (en) * 1978-06-08 1981-01-20 Agence Nationale De Valorisation De La Recherche (Anvar) Perfluoro intermediates and processes for their preparation

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Publication number Publication date
BE674020A (de) 1966-06-20
GB1124078A (en) 1968-08-21
DE1222918B (de) 1966-08-18
DE1222918C2 (de) 1967-03-23
FR1477466A (fr) 1967-04-21
IL24490A (en) 1969-11-12
AT262250B (de) 1968-06-10
CH471085A (de) 1969-04-15
NL6516622A (de) 1966-06-22

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