US3764626A - Method of synthetizing tertiary aliphatic amines by amination of alkyl halides - Google Patents

Method of synthetizing tertiary aliphatic amines by amination of alkyl halides Download PDF

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Publication number
US3764626A
US3764626A US00099853A US3764626DA US3764626A US 3764626 A US3764626 A US 3764626A US 00099853 A US00099853 A US 00099853A US 3764626D A US3764626D A US 3764626DA US 3764626 A US3764626 A US 3764626A
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Prior art keywords
alkyl
amine
process according
reaction
alkyl halide
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US00099853A
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English (en)
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P Pivette
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PIERREFITTE AUBY FR
PIERREFITTE AUBY SA
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PIERREFITTE AUBY SA
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Priority claimed from FR6944604A external-priority patent/FR2071278A5/fr
Priority claimed from FR7044332A external-priority patent/FR2117717A2/fr
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J14/00—Chemical processes in general for reacting liquids with liquids; Apparatus specially adapted therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/24—Stationary reactors without moving elements inside
    • B01J19/2415—Tubular reactors
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00051—Controlling the temperature
    • B01J2219/00074—Controlling the temperature by indirect heating or cooling employing heat exchange fluids
    • B01J2219/00076—Controlling the temperature by indirect heating or cooling employing heat exchange fluids with heat exchange elements inside the reactor
    • B01J2219/00083—Coils

Definitions

  • ABSTRACT This invention is directed to the production, by synthesis, of tertiary aliphatic amines by amination of alkyl haloids, by means of secondary aliphatic amine, wherein a reaction mixture is prepared which consists of two fractions, one fraction comprising at least one alkyl haloid consisting mainly of halogen-l-alkane, the
  • This reaction starts at a preparation step antecedent to the one resulting from the above-mentioned process (a), in that the initial material is nitrile in lieu of amine.
  • the yield is of the same order of magnitude as that of method (a).
  • This reaction takes place under a relatively high pressure of the order of 200 to 300 bars (2,900 to 4,350 psi).
  • R designates an alkyl, X a halide, R and R" low-molecular weight alkyl radicals such as methyl, ethyl, propyl, etc.
  • this reaction takes place in an aqueous medium at temperatures within the range of 50 to 190 C.
  • the pressure normally reached during the reaction is generally of the order of 40 to 50 bars (580 to 725 psi) and may sometimes exceed 80 bars (1,160 psi).
  • This reaction is complete and rapid only if a considerable excess of dialkylamine of the order of 12 to 18 moles per mole of alkyl haloid is used.
  • dialkylamine molar excess is only of the order of 2 to 3 moles per moles of halide, the reaction time requires generally more than 3 hours, thus impairing the economy of the process and the final quality of the resulting tertiary aliphatic amine.
  • the present invention aims at avoiding the inconveniences set forth hereinabove which reside chiefly in the use of relatively high temperatures and pressures during a considerable time period.
  • a reaction mixture is prepared which comprises two fractions, the first fraction consisting of at least one alkyl haloid and comprising a major part of halogen-l-alkane, the other fraction consisting of a secondary aliphatic amine within an aprotic dipolar solvent capable of dissolving both the halide and the secondary amine but not capable of appreciably dissolving, in the cold state, the resulting tertiary
  • aprotic dipolar solvents are capable of dissolving at the same time considerable amounts of alkyl halides and secondary amines as used for the synthesis of tertiary amines, without appreciably dissolving these last-named amines in the cold state. Therefore, the reaction takes place in a homogeneous medium, in contrast with most of the other processes
  • the tertiary amine resulting from the reaction can be extracted or recovered by using a simple physical step consisting, for example, of a decantation which can then be followed by a distillation.
  • the halide is halogenalkane obtained by hydro-halogenation of alphaolefmes, according to a radical or so-called abnormal reaction. It comprises as a rule four to 22 carbon atoms and preferably eight to 18 carbon atoms. Also preferably, bromo-alkanes consisting of a major part of bromo-l-alkane will be selected. However, bromides may be replaced by chlorides. Nevertheless, it should be born in mind that it is much more difficult to obtain chloro-l-alkane of adequate grade from starting mate rials of petroleum origin.
  • Said first fraction of the reaction mixture advantageously contains at least 85 percent by weight of halo- I gen-l-alkane.
  • R and R" are safirated or unsaturated alkyl radicals containing one to 18 carbon atoms and preferably one to four carbon atoms.
  • These secondary amines are symmetric or asymmetric. They consist preferably of dimethylamine, diethylamine, diallylamine, dipropylamine and diethanol amine.
  • reaction is carried out under a pressure above the atmospheric value but below 4 bars (58 psi).
  • Example 1 In a reactor capable of withstanding a pressure of about 2 bars (30 psi) a solution of 360 parts of dimethylamine in 1,200 parts of dimethylformamide is reacted with 1,100 parts of bromo-l-tetradecane prepared by hydrobromidizing tetradecene-l. Within minutes the temperature rises spontaneously to 80 C. Then the temperature is raised to 150 C during 45 minutes, the pressure remaining equal or inferior to 1 bar (14.5 psi) during this period, and then the reagents are allowed to cool to room temperature. The reaction mixture separates spontaneously into two layers.
  • Example 3 In a reactor capable of withstanding a pressure of about 2 bars psi) a mixture consisting of 1,100 parts of tetradecyl bromide containing 95 by weight bromo-l-tetradecane and 1,180 parts of a 32 b.w. dimethylamine solution in N-methylpyrrolidone is stirred.
  • Example 4 In a process similar to the one described in Example 1 and by utilizing n-decyl bromide and dimethylamine dissolved in dimethylformamide, the reagents being used in the same molar proportions as inExample l, a clear, colourless product was separated by decantation and after removal of the head under reduced pressure this product gave substantially pure N- dimethyldecylamine with a 86 yield with respect to alkyl bromide.
  • Example 5 In a flask equipped with an agitator 97 g (1 mole) of diallylamine, 100 g of dimethylformamide and 138.5 g (0.5 mole) of tetradecyl bromide are introduced.
  • the mix is heated during 2 hours, while stirring, to C; the previously homogeneous reaction mixture thus separates into two fractions. These fractions are allowed to cool to room temperature and the stirring is discontinued.
  • the upper layer consisting mostly of N-diallyltetradecylamine was subjected to a fractional distillation under reduced pressure and yielded a high percentage of N-diallyltetradecylamine having a high degree of purity.
  • alkyl haloid utilized was bromide.
  • Advantageous results may also be obtained from chlorides as shown by the following example 6.
  • Example 6 in a reactor capable of withstanding a pressure of about 2 bars (30 psi) a mixture consisting on the one hand of 1,100 parts of a dodecyl chloride containing 93 by weight of chloro-l-dodecane manufactured by chlorinating dodecyl alcohol, and on the other hand of 1,120 parts of a 40 solution of dimethylamine in dimethylformamide was stirred. The temperature increased to 150 C, so that the pressure in the reactor attained 0.7 bars (11.15 psi). The stirring was discontinued and the liquid is allowed to cool to room temperature.
  • the quantity of solvent utilized must be such that all the products and subproducts of the reaction remain in solution throughout the reaction time; as a result, the product obtained by cooling and decantation consists nearly wholly of the formed aliphatic tertiary amine. This result is obtained when the ratio, by weight, of solvent utilized to the alkyl halide input ranges from 2:1 to 5: l.
  • This invention is also applicable to a method permitting of producing tertiary amine as a continuous prosurface-type heat exchanger through which a suitable cooling fluid is circulated, and opens into a decanter 9.
  • This decanter 9 consists of a closed vessel provided at its upper portion with a pipe 10 for exhausting the F h t f being characterized in h t 5 excess dimethylamine in the gaseous state, a lateral tion mixture circulated and exposed during 1ts clrcu- Outlet pipe 11 leading from the upper portion of the 13mm t a gradually mcreasmg telnperamre and that canter for recovering the crude tertiary amine formed the ratio of solvent to the alkyl halide ranges from 2:1 in the liquid State, and, at the bottom another pipe 12 to 5:1 by welght the macho Product h Subse' bent to an S shape (turned about 90in its plane) for q h y then decanted cohtmuously P 10 discharging the bottom solution of dimethylamine hyeratlhg decahtmg Vesseldrobromide in dimethylformamide.
  • the pressure may be kept at a value below adjusted by means of suitable metering pumps (not 2 bars (about 30 psi) so that the necessary apparatus Shown).
  • the reaction mixture is taken from the top of is simplified with the additional advantageous feature the C lumn and directed through the cooler 8 to the that the process may be carried out in a suitable glass continuously operating decanter 9 where the amine is or plastic apparatus, so that pollutions by metal salts r vered in th upper phase with a degree of purity can safely be avoided. approximating the impurities being ascribable By way of example, the continuous manufacturing chlefly to the 1n1t1almater1als.
  • the method of this invention may be Carried ut in an ppa-
  • the rate of feed of the raw materials corresponds to ratus of the type illustrated diagrammatically in the sina e ti n ti of 4 t 15 mi ute gle FIGURE of the attafmed drawmg' 40
  • the molar ratios of secondary amine to alkyl halide This apparatus comprrses a reactor 1 conslstmg ofha are within the range of 2:1 to vemcal colufmn g zfl i t???
  • a hlelg t The'amounts of solvent utilized are by weight in the a f T proportion of 211 to 5:1 by weight of the alkyl halide 2 1s prov1ded w1th a plurahty of heating elements 3 such input as coil tubes or the like disposed at spaced intervals 5 Ali] h th d t b d along the longitudinal axis of the column and supplied h t oug e i amlne exces 0 t 1 with heating fluid at different temperatures so that the l lg i re atwe y reacuon fa e 18 re temperature within the reaction column 2 increases uve y lg from bottom to top.
  • the column 2 y emerge from the eohdults 12 and the comains fining bodies (not shown) Such as R hi actlon by-products as well as the solvent are recovered rings.
  • This column 2 is fed from the bottom whereby and e ye y ll h e Suitable means alkyl bromide is supplied through a conduit 4, dimethnot wlthlh the Scope of the lhvehtlohylformamide through another conduit 5 and dimethyl-
  • the following table gives the numerical data conamine through a branch conduit 6 leading into conduit cerning eight tests of continuous tertiary amine produc- 5, as shown, tion according to the method of this invention, the sol- A complementary conduit 7 leads from the top of vent consisting in all cases of dimethylformamide, and column 2 down into a cooling device 8 consisting of the secondary amine consisting of dimethylamine.
  • P X 100/p wherein P denotes the total weight of pure tertiary amine contained in the resultant crude amine, and p the weight of amine to be theoretically obtained from the bromo -l-alkane contained in the crude alkyl bromide utilized.
  • a process for the continuous production of aliphatic tertiary amines comprising circulating together in a reactor at least one alkyl hads s tin ssenti ly ha -7 1 9: les
  • one aliphatic secondary amine and at least one anhydrous organic solvent adapted to dissolve the raw materials and the byproducts of the reaction and not appreciably dissolve in the cold state the resulting aliphatic tertiary amine, said solvent being selected from the group of dipolar aprotic solvents comprising dimethyl formamide, hexamethyl phosphorotriamide, tetrahydrofuran and N-rnethylpyrrolidone,
  • alkyl halide is a halo-l -alkane produced by hydrohalogenation of olefins according to a radical reaction.
  • portion of secondary amine and alkyl halide is such that there is a molar ratio of at least two molecules of secondary amine to one molecule of alkyl halide.
  • reaction mixture is kept at a pressure below 2 bars while it is subjected to a progressively increasing temperature.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US00099853A 1969-12-23 1970-12-21 Method of synthetizing tertiary aliphatic amines by amination of alkyl halides Expired - Lifetime US3764626A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR6944604A FR2071278A5 (en) 1969-12-23 1969-12-23 Tertiary aliphatic amine production by - amination of alkyl halides
FR7044332A FR2117717A2 (en) 1970-12-09 1970-12-09 Tertiary aliphatic amine production by - amination of alkyl halides

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US (1) US3764626A (fr)
JP (1) JPS5339403B1 (fr)
BE (1) BE760696A (fr)
CH (1) CH529095A (fr)
DE (1) DE2062548C3 (fr)
ES (1) ES386744A1 (fr)
GB (1) GB1337285A (fr)
LU (1) LU62297A1 (fr)
NL (1) NL170728C (fr)
SE (1) SE371814B (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3852258A (en) * 1972-12-18 1974-12-03 Chevron Res Process for preparing polyolefin substituted amines
US4618718A (en) * 1985-06-14 1986-10-21 Halocarbon Products Corporation Preparation of trifluoroethylamine
US5347053A (en) * 1992-11-04 1994-09-13 Albemarle Corporation Process for preparing alkylamines

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3471561A (en) * 1966-03-28 1969-10-07 Baird Chem Ind Amination of alkyl halides
US3491151A (en) * 1967-07-11 1970-01-20 Polaroid Corp Preparation of alkylated hydroxylamines
US3542876A (en) * 1968-09-26 1970-11-24 Procter & Gamble Amination of alkyl halides

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3471561A (en) * 1966-03-28 1969-10-07 Baird Chem Ind Amination of alkyl halides
US3491151A (en) * 1967-07-11 1970-01-20 Polaroid Corp Preparation of alkylated hydroxylamines
US3542876A (en) * 1968-09-26 1970-11-24 Procter & Gamble Amination of alkyl halides

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3852258A (en) * 1972-12-18 1974-12-03 Chevron Res Process for preparing polyolefin substituted amines
US4618718A (en) * 1985-06-14 1986-10-21 Halocarbon Products Corporation Preparation of trifluoroethylamine
US5347053A (en) * 1992-11-04 1994-09-13 Albemarle Corporation Process for preparing alkylamines

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Publication number Publication date
NL170728C (nl) 1982-12-16
JPS5339403B1 (fr) 1978-10-21
SE371814B (fr) 1974-12-02
NL7018610A (fr) 1971-06-25
LU62297A1 (fr) 1972-08-23
GB1337285A (en) 1973-11-14
ES386744A1 (es) 1974-04-01
DE2062548A1 (de) 1971-06-24
NL170728B (nl) 1982-07-16
CH529095A (fr) 1972-10-15
DE2062548B2 (de) 1979-02-22
DE2062548C3 (de) 1979-10-11
BE760696A (fr) 1971-06-22

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