US3471561A - Amination of alkyl halides - Google Patents

Amination of alkyl halides Download PDF

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Publication number
US3471561A
US3471561A US537708A US3471561DA US3471561A US 3471561 A US3471561 A US 3471561A US 537708 A US537708 A US 537708A US 3471561D A US3471561D A US 3471561DA US 3471561 A US3471561 A US 3471561A
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reaction
amine
alkyl
alkaline material
dimethylamine
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US537708A
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Zaven A Dadekian
David S Wilbourn
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Baird Chemical Industries Inc
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Baird Chemical Industries Inc
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
    • C07C209/06—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of halogen atoms
    • C07C209/08—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of halogen atoms with formation of amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings

Definitions

  • This invention relates to the amination of alkyl halides to form tertiary amines. More specifically, the instant invention teaches a process for aminating higher alkyl chlorides preferably having from 4 to 22 carbon atoms with secondary amines such as dimethylamine. These tertiary amines are useful for the preparation of surface active agents.
  • the rate at which the alkaline material is added is related to the rate of formation of the amine hydrohalide.
  • the amine hydrohalide is formed by the reaction of the excess amine with the hydrohalide evolved from the basic reaction between the amine and the alkyl halide.
  • the alkaline material is added at a rate sufiicient to convert the amine hydrohalide back to the free amine as it is formed, but not so rapidly as to permit the accumulation of a substantial excess of the alkaline material. This procedure serves to make available the maximum amount of free amine, a factor favorable to the desired reaction, while minimizing the formation of the aforesaid undesired by-products by eliminating excess alkaline material.
  • the alkaline material is suitably added continuously over the course of the first 1% hours of the reaction, a period in which over of the reaction takes place.
  • a substantially constant rate of addition for about one hour gives the desired result if the addition commences about 15 minutes after a significant rate of reaction begins.
  • reaction is carried out in a two phase system. Sufficient water must be present to dissolve the bulk of the salt formed during the reaction. If less water is used salt accumulates and complicates phase separation and handling. Generally at least one and onehalf parts by weight of water are present for each part of salt. From two to four parts of water are preferable.
  • R is an alkyl group having from 4 to 22 carbon atoms, preferably from 8 to 18. It may be straight or branched chain with an odd or even number of carbon atoms. R and R are alkyl groups having from 1 to 4 carbon atoms, preferably, 1 to 2, X is a halide group, such as iodide, chloride, or bromide, most preferably the chloride.
  • the tertiary amines of the instant invention include octyl dimethylamine, dodecyl dimethylamine, tridecyl dimethylamine, heptadecyl dimethylamine, octadecyl dimethylamine, hexyl diethylamine, pentadecyl diethylamine, decyl dipropylamine, dodecyl dibutylamine, eocyl methylethylamine, nonyl ethylpropylamine and undecyl methylpropylamine.
  • the reaction is exothermic and the rate of reaction is a function of the temperature, the molecular weight of the alkyl group and the particular halide. At a constant temperature the lower molecular weight alkyl compounds are the more reactive. Iodides are more reactive than the bromides; the bromides more reactive than the chlorides.
  • the reaction temperature may be from 50 to 190 0, most preferably, from 80 to C. After the reaction is almost complete, it is often desirable to heat the reactor to a higher temperature, e.g., from 140 to C., for a period of 15 min. to 3 hrs. to insure complete reaction. When the reactor is heated to reaction temperature an exotherm will occur. At this time the addition of the alkaline material may be commenced.
  • the pressure is 125 to 225 p.s.i. during the course of the reaction and the reaction time may vary from 3 to 8 hrs. depending on the particular reactants employed.
  • the alkaline materials which may be employed are the soluble inorganic strong bases such as metal hydroxides, carbonates and bicarbonates, and, also the basic metal oxides and salts. Such materials may be readily selected by those skilled in the art.
  • Preferred materials are the alkali and alkaline earth metal hydroxides. These include sodium hydroxide, potassium hydroxide and calcium hydroxide. As a matter of convenience these materials may be added to the reaction mass as a 10 to 50% aqueous solution.
  • Sufiicient alkaline material is employed to neutralize the amine hydrohalide formed in the reaction. A slight molar excess is advantageous to insure that no amine hydrohalide is left unconverted to free amine in the system. At the end of the reaction an excess of alkaline material is not detrimental.
  • EXAMPLE I The amination is conducted in a 2300-gallon, stainless steel clad, 500 p.s.i. internal reactor. The agitator is turned on prior to the charging of reactants. Dodecyl chloride is pumped in from a storage tank until 35 moles are fed to the reactor. After charging the dodecyl chloride, a 50% aqueous solution of dimethylamine is charged until 70 moles are fed. This is a 2:1 molar ratio of the amine to the chloride or a 100% molar excess. During the charging of the dimethylamine, heat is applied to bring the temperature up to 116 C. At the end of the dimethylamine charge and when the batch is up to the 116 C. temperature, a solution of 50% of sodium hydroxide is pumped into the batch at a constant rate of 5l#/min. in the interval of one hour. A molar excess is added based on the dimethylamine hydrochloride formed.
  • the batch is maintained on automatic temperature control during which the heat from the exothermic reaction is taken away from the batch with cold water in the coil. Little cooling is required after the first one and one half hours, since the reaction is almost complete. After three hours the batch temperature is raised to 140 C. with steam in the coil, and maintained there for fifteen minutes. This final heating at high temperature insures complete reaction. The batch is then cooled to 260 F. and agitation is turned off. The batch is allowed to settle in the reactor for fifteen minutes, during which time it separates into an amine and salt water phase, both saturated with dimethylamine.
  • EXAMPLE II The procedure described in Example I is repeated with n-octyl chloride and stearyl chloride. In both cases the same reaction conditions are used. The n-octyl dimethylamine and stearyl dimethylamine are obtained in yields of 95% and 92%, respectively. The product quality after flash distillation is about 97% of the alkyl dimethylamine meeting an APHA 25 color specification.
  • a process for the amination of an alkyl halide which comprises: reacting an alkyl halide, wherein said halide is a chloride, bromide or iodide, with 60 to 300% of a molar excess of a lower dialkyl secondary amine in a two phase aqueous-organic system at a temperature from 50 to C., and thereby evolving an amine hydrohalide; adding an alkaline material continuously over the course of the first one and one-half hours of said reaction so as to form, with said amine hydrohalide as it is evolved, a halide salt of said alkaline material, such continuous addition being controlled so as to prevent the formation of a substantial excess of said alkaline material, at least one and one-half to four parts by weight of water being present for each part of said salt in said aqueous-organic system to dissolve the bulk of said salt; and thereafter recovering the aminated product.
  • alkyl halide is an alkyl chloride having 4 to 22 carbon atoms.
  • alkyl halide is an alkyl chloride
  • the secondary amine is a dialkylamine
  • the molar excess of the amine is about 2 to 1
  • the alkaline material is an alkali metal hydroxide.
  • alkyl halide is a mixed alkyl chloride having from 11 to 15 carbon atoms.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US537708A 1966-03-28 1966-03-28 Amination of alkyl halides Expired - Lifetime US3471561A (en)

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US53770866A 1966-03-28 1966-03-28

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US (1) US3471561A (cs)
BE (1) BE696150A (cs)
DE (1) DE1593770B2 (cs)
FR (1) FR1515601A (cs)
GB (1) GB1130069A (cs)
LU (1) LU53289A1 (cs)
NL (1) NL6704211A (cs)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3742060A (en) * 1969-11-24 1973-06-26 Gulf Research Development Co Preparation of amines
US3764626A (en) * 1969-12-23 1973-10-09 Pierrefitte Auby Sa Method of synthetizing tertiary aliphatic amines by amination of alkyl halides
WO1987000831A1 (en) * 1985-08-08 1987-02-12 The Dow Chemical Company Preparation of an allyl amine and quaternary diallyl ammonium compounds therefrom
US5347053A (en) * 1992-11-04 1994-09-13 Albemarle Corporation Process for preparing alkylamines

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE761985A (fr) * 1970-10-19 1971-07-01 Recordati Chem Pharm Procede de preparation de n-alcoyl-dimethylamines

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3299142A (en) * 1963-05-27 1967-01-17 Phillips Petroleum Co Preparation of alkyl amines

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3299142A (en) * 1963-05-27 1967-01-17 Phillips Petroleum Co Preparation of alkyl amines

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3742060A (en) * 1969-11-24 1973-06-26 Gulf Research Development Co Preparation of amines
US3764626A (en) * 1969-12-23 1973-10-09 Pierrefitte Auby Sa Method of synthetizing tertiary aliphatic amines by amination of alkyl halides
WO1987000831A1 (en) * 1985-08-08 1987-02-12 The Dow Chemical Company Preparation of an allyl amine and quaternary diallyl ammonium compounds therefrom
AU578545B2 (en) * 1985-08-08 1988-10-27 Dow Chemical Company, The Preparation of an allyl amine and quaternary diallyl ammonium compounds
US4946996A (en) * 1985-08-08 1990-08-07 The Dow Chemical Company Preparation of an allyl amine and quaternary diallyl ammonium compounds therefrom
US5347053A (en) * 1992-11-04 1994-09-13 Albemarle Corporation Process for preparing alkylamines

Also Published As

Publication number Publication date
DE1593770B2 (de) 1976-06-16
FR1515601A (fr) 1968-03-01
DE1593770A1 (de) 1972-03-30
NL6704211A (cs) 1967-09-29
GB1130069A (en) 1968-10-09
LU53289A1 (cs) 1967-05-28
BE696150A (cs) 1967-09-01

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