US2693494A - Isopropyl-aryl compounds chlorinated in the isopropyl radical and process of making same - Google Patents

Isopropyl-aryl compounds chlorinated in the isopropyl radical and process of making same Download PDF

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Publication number
US2693494A
US2693494A US791172A US79117247A US2693494A US 2693494 A US2693494 A US 2693494A US 791172 A US791172 A US 791172A US 79117247 A US79117247 A US 79117247A US 2693494 A US2693494 A US 2693494A
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mixture
tetrachloracetone
isopropyl
parts
symmetrical
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Geiger Max
Usteri Eduard
Graenacher Charles
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BASF Schweiz AG
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Ciba AG
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
    • C07C17/263—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions
    • C07C17/2637—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions between a compound containing only oxygen and possibly halogen as hetero-atoms and a halogenated hydrocarbon
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
    • C07C17/32—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by introduction of halogenated alkyl groups into ring compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C22/00—Cyclic compounds containing halogen atoms bound to an acyclic carbon atom
    • C07C22/02—Cyclic compounds containing halogen atoms bound to an acyclic carbon atom having unsaturation in the rings
    • C07C22/04—Cyclic compounds containing halogen atoms bound to an acyclic carbon atom having unsaturation in the rings containing six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C25/00—Compounds containing at least one halogen atom bound to a six-membered aromatic ring
    • C07C25/02—Monocyclic aromatic halogenated hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C25/00—Compounds containing at least one halogen atom bound to a six-membered aromatic ring
    • C07C25/18—Polycyclic aromatic halogenated hydrocarbons
    • C07C25/22—Polycyclic aromatic halogenated hydrocarbons with condensed rings

Definitions

  • isopropyl-aryl compounds chlorinated in the isopropyl radical are made in a simple manner by condensing an aromatic compound consisting of at most two condensed siX-membered nuclei which are free from substituents which contain easily replaceable atoms, form salts, and have a predominantly meta-directing effect, in the presence of aluminum chloride, with a chlorinated acetone corresponding to the general formula wherein at least one X and at most two Xs represent chlorine atoms and the remaining Xs represent hydrogen atoms.
  • aromatic compounds there may be used compounds consisting of at most two condensed six-membered nuclei which are free from substituents which contain easily replaceable atoms, form salts and have a predominantly meta-directing effect.
  • aromatic compounds of the benzeneand naphthalene series which contain substituents with easily replaceable atoms, such as CPl -halogen-groups, or substituents which form salts, such as OH-, NH2-, NH-acyl- N(alkyl) -groups, or substituents which have a predominantly meta-directing effect, such as NO COOH-, CN-, CCl CO-, SO I-I- or 'SCN-groups.
  • aromatic hydrocarbons free from alkyl groups, such as, for example, benzene or naphthalene; further there may be used aromatic hydrocarbons substituted by one or more alkyl groups, alkoxy groups or halogen atoms, such as, for example, toluene, ethylbenzene, xylenes, tertiary-butylbenzene, anisole, chlorobenzene, ortho dichlorobenzene, 2:4 dichlorotoluene, alpha-chloronaphthalene and the like.
  • alkyl groups such as, for example, benzene or naphthalene
  • aromatic hydrocarbons substituted by one or more alkyl groups, alkoxy groups or halogen atoms such as, for example, toluene, ethylbenzene, xylenes, tertiary-butylbenzene, anisole, chlorobenzene, ortho dichlorobenzene, 2:
  • the condensation products so obtained correspond to the general formula wherein at least one Z and at most two Zs represent an aromatic radical consisting of at most two condensed six-membered nuclei free from substituents which contain easily replaceable atoms, form salts and have a predominantly meta-directing eifect, and the remaining Z stands for a chlorine atom, and wherein at least one X and at most two Xs represent chlorine atoms and the remaining Xs represent hydrogen atoms.
  • condensation products obtained as described above are either crystalline compounds or viscous oils, which can be used as intermediate products for a very wide variety of purposes and also for the production of agents for combating pests, or which themselves find application as agents for combating pests.
  • Example 1 CHClz boils at 120-122" C. under a pressure of 0.22 mm., and is a colorless, almost odorless oil.
  • Example 2 230 parts of 1:1:3:3-tetrachloracetone and 86 parts of chlorobenzene are mixed-in the course of 3 hours with 100 parts of aluminum chloride at C. to 2 C. while stirring Well. The reaction mixture is then further stirred for hours longer in an ice bath. The dark viscous mass is then poured on to ice, taken up in ether, and washed neutral. After drying the ethereal solution and evaporating the ether the excess of tetrachloracetone is distilled at about 70 C.
  • Example 3 11 parts of aluminum chloride are introduced in the course of 2 hours, while stirring well and cooling with ice, into a mixture of 16 parts of 121:1:3-tetrachloracetone and 18 parts of chlorobenzene. The whole is then stirred at 0-2 C. for a further 22 hours, the dark viscous reaction product is decomposed with ice, taken up in ether, Washed neutral with Water, and filtered to remove insoluble White flocks. By distillation a small quantity of chlorobenzene and tetrachloracetone is recovered from the crude product.
  • the asymmetrical penta-chlorisopropylwpara-chlorobenzene corresponding to the formula Gaga...
  • Example 4 70 parts of benzene and 15 parts of a mixture of symmetrical and asymmetrical tetrachloracetone are mixed in the course of 3 hours with 10 parts of aluminum chloride, while stirring at 0-5 C. The whole is then further stirred in an ice bath for 20 hours.
  • the dark reaction mass is poured onto ice and the oily layer taken up in benzene.
  • the benzene solution is washed with water until neutral and dried, whereupon the solvent is distilled off.
  • the mixture of the isomeric pentachlorisopropyl benzenes is rectified in a vacuum. It boils at 173-176 C. under a pressure of 15 mm. mercury.
  • Example 5 4.5 parts of aluminum chloride are introduced in the course of one hour at -10 C. to -l5 C., while stirring, into a mixture of 50 parts of toluene and 20 parts of 1:1:3:3-tetrachloracetone. The mixture becomes dark in color.
  • the reaction mass is decomposed with acidified icewater, and extracted with a solvent, for example, toluene. After drying, the solvent is distilled. The residue is fractionated under greatly reduced pressure. After being distilled twice the resulting pentachlorisopropyl-toluene boils at 114-116 C. under a pressure of 0.02 mm. in the form of a colorless viscous oil.
  • Example 6 4.5 parts of aluminum chloride are introduced at 10 C. to -15 C. in the course of one hour, while stirring into a mixture of 50 parts of anisole and 20 parts of 1:1:3:3-tetrachloracetone. After stirring for 7 hours at l0 C. to -15 C. the dark reaction mass is decomposed with acidified ice-water, the oily layer is washed with water and dried. The excess of anisole and unreactecl tetrachloracetone are then removed by distillation under reduced pressure, and the residue is fractionated under greatly reduced pressure. The resulting pentachlorisopropyl-anisole boils at 161-165 C. under a pressure of 0.03 mm. and melts, after recrystallisation from petroleum ether, at -102 C.
  • Example 7 13 parts of aluminum chloride are introduced in the course of 2 hours at 0C. to 5 C., While stirring, into a mixture of 100 parts of anisole and 20 parts of 1:1:3 :3- tetrachloracetone. The dark mixture is stirred for 20 hours at the same temperature, and then decomposed with ice and dilute hydrochloric acid. The oily layer is separated, washed with water, dried, and the excess of anisole is distilled under reduced pressure. The distillation residue solidifies in crystalline form. It is purified by recrystallisation from a mixture of chloroform and methanol. The bis-dichloromethyl-bis-anisyl-methane so obtained melts at 148-149 C.
  • Example 8 4.5 parts of aluminum chloride are introduced in the course of one hour at 10.C. to 15 C., while stirring, into amixture of 60 parts of a-chloronaphthalene and 20 parts of 1:1:3:3-tetrachloracetone. After stirring at -10 C. to l5 C. for 6 hours, the reaction mass is decomposed with acidified ice-water, and the oily layer is separated, washed with water and dried. The excess of a-chloro-naphthalene is then distilled under reduced pressure, and the residue is fractionated under greatly reduced pressure. After the second distillation, 'the resulting pentachlorisopropyl-a-chloronaphthalene boils at l85187 C. ,under a'pressure of 0.02 mm. in the form of a very viscous oil.
  • an aromatic compound selected from the group consisting of benzene, naphthalene and their alkyl, alkoxy and halogen derivatives, which aromatic compound contains at least one hydrogen atom linked to a nuclear carbon atom,
  • aromatic compound selected from the group consisting of benzene, naphthalene and their alkyl, alkoxy and halogen derivatives, which aromatic compound contains at least one hydrogen atom linked to a nuclear carbon atom
  • a process for the manufacture of a mixture of the penta-chlorisopropyl benzenes by condensing benzene at a temperature of 15 C. to +5 C. with a mixture of symmetrical and asymmetrical tetrachloracetone in the presence of, as further reactant, about /a1 mol of aluminum chloride for each mol of mixture of symmetrical and asymmetrical tetrachloracetone.
  • a process for the manufacture of a mixture of the penta-chlorisopropyl toluenes by condensing toluene at a temperature of -15 C. to +5 C. with a mixture of symmetrical and asymmetrical tetrachloracetone in the presence of, as further reactant, about /a--1 mol of aluminum chloride for each mol of mixture of symmetrical and asymmetrical tetrachloracetone.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US791172A 1946-12-18 1947-12-11 Isopropyl-aryl compounds chlorinated in the isopropyl radical and process of making same Expired - Lifetime US2693494A (en)

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CH262165T 1946-12-18

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US (1) US2693494A (enrdf_load_stackoverflow)
CH (3) CH262166A (enrdf_load_stackoverflow)
DE (1) DE840684C (enrdf_load_stackoverflow)
FR (1) FR957268A (enrdf_load_stackoverflow)
GB (1) GB648862A (enrdf_load_stackoverflow)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1961397A (en) * 1927-07-14 1934-06-05 Schering Kahlbaum Ag Preparing of a new condensation product from meta-cresol and acetone
US2430822A (en) * 1944-04-28 1947-11-11 Atlantic Refining Co Chlorination of isopropylbenzenes
US2455643A (en) * 1944-03-25 1948-12-07 Shell Dev Condensation products from ketones and aralkyl organic compounds and method for producing the same

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1961397A (en) * 1927-07-14 1934-06-05 Schering Kahlbaum Ag Preparing of a new condensation product from meta-cresol and acetone
US2455643A (en) * 1944-03-25 1948-12-07 Shell Dev Condensation products from ketones and aralkyl organic compounds and method for producing the same
US2430822A (en) * 1944-04-28 1947-11-11 Atlantic Refining Co Chlorination of isopropylbenzenes

Also Published As

Publication number Publication date
CH262166A (de) 1949-06-15
GB648862A (en) 1951-01-17
FR957268A (enrdf_load_stackoverflow) 1950-02-17
CH256845A (de) 1948-09-15
CH262165A (de) 1949-06-15
DE840684C (de) 1952-06-05

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