DE2363324C3 - Process for the preparation of tertiary amines - Google Patents

Description

, The partial pressure
ponoxide can be found in ^

beüage * jcweik ^ s ^ Ä generally the erfindungsgemaB _m used catalytic converters

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overall reaction
achieved; the reacti
medium and reaction partner volume) from 10 to 90 and 90 to / o The reaction conditions and the activity together 'tSSZc ^^ JglS ^ degree of conversion of the olefin and the selectivity towards

Mense of used OHto S ₁ ! betragec without ever 60%

This means that ^{the results of the previously} known example 5 * * «■ Rector were! 0 cm 'of ethanol, 6.7 g

£? ^ / 2? ^ ^{The whole became} " ¹ ^

"5? £ ° Γί ^ - ^" * ^{6 h heated to 14 ° C. The} heptyldimethylamines were obtained with a selectivity of? ^Ι Λ, based on hexene-1; the conversion

^{6 7}

Example 6

In general, the implementation is carried out as follows:

A reactor with gas inlets, stirrer and heating device is charged one after the other with olefin solvent, catalyst and amine. Then ..... λ ■ '-menmonoxide and then hydrogen introduced under partial pressures. The whole stirring is brought to the desired temperature. After cooling and releasing the pressure in the device, the reaction mixture is analyzed by gas chromatography and the amount of olefin consumed and substituted amine formed is determined. The degree of conversion for olefin and the selectivity for amine are then calculated from this.

The following examples serve to provide a more detailed explanation.

example 1

6.7 g of hexene-1, 10 cm ^{3 of} toluene, 0.1 g of Rh (CO), Cl (p-toluidine) and 3.6 g of dimethylamine were placed in a reactor. The mixture was heated to 150 ° C. for 5 h under a pressure of 60 bar CO and 60 bar hydrogen while stirring. The heptyldimethylamines were obtained with a selectivity of 98%, based on hexene-1, the conversion rate of hexene-1 being 100%.

Example 2

The procedure was as in Example 1, but with partial pressures of 30 bar each for CO and H ₈ . The degree of conversion for hexene-1 was also 100%, but the selectivity with regard to the amines was only 81%, based on hexene-1.

Example 3

^{10 cm 3 of} toluene, 6.7 g of hexene, 0.1 g of RhCl ₃ [S (CjHs) J ,, and 3.6 g of dimethylamine were placed in a reactor and the mixture was stirred for 5 hours under a pressure of 60 bar CO and 60 bar H ₄ heated to 150 ⁰ C. The Heptyldimethylmaine were obtained with a selectivity of 97% based on hexene-I, obtained; the degree of conversion for hexene-1 was 100%.

Example 4

The procedure was as in Example 3, but under partial pressures of 30 bar each for CO and -H ₁ . The degree of conversion for hexene was 100%; the Se * charged. The mixture was _{heated to 200 ° C. for 5 h under 90 bar H 2} and 30 bar CO. The heptlydimethylamines were obtained in a selectivity of 83%, based on hexene-1; the degree of conversion of witches was 44%.

a ₅ example 7

^{10 cm 3 of} ethanol, 6.7 g of hexene-1, 3.6 g of dimethylamine and 0.00046 g of Rh (DMGH) _x (DMGH stands for dimethylglyoximato-anion) were placed in a reactor. The mixture was heated ^{to 150 °} C. under 90 bar H and 30 bar CO for 5 h. The heptyldimethylamines were obtained in a selectivity of 67%, based on hexene-1; the degree of conversion for hexene was 68%.

Example 8

6.7 g of hexene-1, 3.6 g of dimethylamine and a catalyst consisting of the freshly prepared mixture of 1 cm ^{3 of} a toluene solution containing 6 × 10 ⁴ g of [Rh (CO) ₂ Cl] ₂ and from I cm ⁹ toluene solution containing 5 - charged with 10 ~ ⁴ g of dimethylsulfoxide such a mixture ent-- · - · "substantially

0.0010 g Rh (CO) CI (OSv £ u

The reaction was in IO cm ³ of toluene at 150 ⁰ C ^under ^ ^'βΓ ^ ¹ ^ ⁰ ^ ^and performed ar CO for 5 h. The heptyldimethylamines were obtained in a selectivity of 68%, based on hexene-1; the degree of conversion of hexene-1 was 96%.

Example 9

6.7 g of hexene-1, 3.6 g of dimethylamine, 10 cm ^{3 of} ethanol and 0.141 g of RuCl ₈ - _JS [P (OC _e Hs),] _{4 were placed} in a reactor. The mixture was heated ^{to 150 °} C. under 60 bar H ₁ and 60 bar CO for 5 h. The heptyldimethylamines were obtained in a selectivity of 91%, based on hexene-1, whose degree of conversion was 89%.

. .

Example ιυ

6.7 g of hexene-1, 3.6 g of dimethylamine, 10 cm * ethanol and 0.038 g of RuCljCO ₈ - (pyridine) were placed in the reactor and the mixture was placed under 60 bar of H _{8 6j} . _and ^ ₀ ^ _{GO 45 h to 160} o _{c increases} 2 _{t D} j _e heptyl

dimethylamines were obtained in a selectivity of 77%, based on hexene-1, whose conversion degree was 29%.

Example 11

A mixture of 6.7 g of hexene-1, 3.6 g of dimethylamine, 10 cm ^{3 of} ethanol and 0.03! rg RuCl ₂ (CO) ₂ - (bipyridine) was heated ^{to ISO 0} C under 60 bar H ₁ and 60 bar CO for 5 h. The heptyldtmethylamines were formed with a selectivity of 68%, based on hexene-1, the degree of conversion of which was 23%.

Example 12

A complex connection was produced by passing carbon monoxide through a boiling ethanolic solution of RuCl _s , 3 H ₁ O, according to the method described by Stephensen et al (J. Inorganic Nuclear Chemistry [1966] 28,951). This solution contained 0.407 g of ruthenium in 50 cm ³ .12.5 cm ^{3 of} this solution were ^{mixed with 0.21 cm 3 of} dimethyl sulfoxide and a cliquot of the resulting solution containing 0.1 mg of atom Ru as complex compound was used as a catalyst. The catalyst defined in this way was placed in a reactor with 6.7 g of 1-hexene and 3.6 g of dimethylamine and the reaction was carried out in ethanol at 150 ^° C. for 5 h under 90 bar of H ₂ and 30 bar of CO. The heptyldimethylamines were obtained in a selectivity of 84%, based on hexene, the degree of conversion of which was 60%.

Example 13

6.7 g of hexene-1, 3.6 g of dimethylamine, 10 cm ^{3 of} ethanol and 0.141 g of Pt [P- (OC ₆ Hs) _{3 I 4} were placed in a reactor and the mixture was added for 5 h

60 bar H ₂ and 60 bar of CO at 200 ⁰ C were heated The Heptyldimethylamine in a selectivity of

61% obtained, based on hexene-1, its degree of conversion was 12%.

Example 14

A mixture of 6.7 g of hexene-1, 3.6 g of dimethylamine, 10 cm ^{3 of} ethanol and 0.08 g of PdCl ₂ [P (OC ₆ H ₅ ) _{I] 2} was under 60 bar hydrogen and 60 bar CO for 5 h heated to 150 ⁰ C. The heptyldimethylamines were obtained in a selectivity of 62%, based on hexene-1, the degree of conversion of which was 38%.

Example 15

An ethanolic solution of butene-1 containing 4.5 g of butene-1 and 10 cm ^{3 of} ethanol was placed in a reactor. Subsequently, 3.6 g of dimethylamine and

ei [P (OC _e H _s ) ₃ ] ₂ charged. The mixture was heated to 200 ° C. under 60 bar CO and 60 bar hydrogen for 3 h. The nonadecyldimethylamines were obtained in a selectivity of 97%, based on octadecene-1, the degree of conversion of which was 98%.

Example 18 6.7 g of hexene-1, 10 cm ³ Ethanol, 10.3 g dibutylamine and 0.1 g Rh (CO) ₂ Ck

(p-toluidine) and the mixture is heated to 150 ^° C. for 1 h under 60 bar CO and 60 bar H ₂

Heptyldibutyiatnine were found in a selectivity of

98% obtained, based on hexene-1, whose conversion

degree of efficiency was 100%.

Example 19

6.7 g of hexene-1, 10 cm ^{3 of} ethanol, 6.8 g of piperidine and 0.1 g of RhCOCl [P (OC _e ^ao H _s ) ₃ ] ₂ were placed in a reactor and under 60 bar of CO and 60 for 3 h bar H ₂ heated to 150 ^{0 C.} The heptylpiperidines were obtained with a selectivity of 98%, based on hexene-1, the degree of conversion of which was 97%.

added and the whole for 30 minutes under 60 bar _H2 and 60 bar of CO at 150 ⁰ C The heated Amyldiinethylamine were obtained in a yield of 97% based on 1-butene.

Example 16

The procedure was as in Example 15, instead of Butene-1 was replaced by 13.5 g of oleodecane-1. the Tridecyldimethylamines were obtained in a selectivity of 98%, based on Bodeeen-1, its Degree of conversion 10G>% fraud.

Example 17

_ A reactor was filled with 20.2 g of octadecene-1, 10 cm ^{3 of} ethanol, 6 g of dimethylamine and 0.1 g of Rh (CQ) -

Examples 20 to 38

A number of examples were carried out with a catalyst containing an amine as ligand. For this, 6.7 g of 1-hexene, 10 cm ^{3 of} ethanol, 3.6 g of dimethylamine and the catalyst were placed in the reactor. The catalyst had been obtained by mixing 1 ^cm3 toluene solution containing 0.020 g of [Rh (CO) ₂ Cl] ₂ (10- ⁴ moles) containing 1 cm ³ of a toluene solution containing 2 x 10 "* mol one of the This mixture corresponds to 2 · 10- * moles of complex compound [Rh (CO) ₂ Cl · amine]. The mixture was ^{heated to 150 °} C. for 5 hours while stirring, with 60 bar of hydrogen and 60 bar of CO being injected. After cooling and degassing, the reaction mixture obtained was analyzed by means of vapor phase chromatography. The results are as follows:

Example ♦ 5 game

Ligand

so 20 CH ₃ NH ₂

21 C ₂ H ₅ NH ₂

22 C ₈ H ₁₇ NH ₂

23 a-naphthylamine

24 dibutylamine
SS 25 dioctylamine

26 triethylamine

27 octodecylamine

28 N-methylpiperidine

29 aniline

30 dimethylamine

31 diisopropylamine

32 di- (ethylhexyl> amine

33 dipropylamine

34 diphenylamine
35 dinonylamine

36 tributyiamine

37 dimethylaniline

38 cyclohexylamine

Conversion selectivity degree of fitness, for heptyl based dimethylamine on witches (» 100 95 95 98 97 95 95 95 100 96 97 97 100 95 94 98 97 98 94 93 94 96 97 99 98 95 93 98 90 95 99 97 98 93 96 94 97 96

Claims (1)

1 2 The various known ones listed above w. claim: procedures carry out all doing formation of a sizeable ^ - Amount of unwanted by-products. This disadvantage Process for the preparation of tertiary amines ^; ynide has been confirmed in general works such as "Carbon Monoxide in V by Reacting Olefins with Carbon Monoxide, 5 Organic Synthesis" by Falbe. These competing by-products of hydrogen and carbon monoxide, which occur in hydrogen and secondary amines with partial considerable amounts, are above all aldehydes, alcohols from 10 to 120 bar at a temperature of 60 to and amides, with the aldehydes still below the reaction 2gjQ ° C for 10 min up to 10 r. can condense with one another in the presence of a coordination complex compound of a Me- io. For all these reasons, the observed selectivity in Group VIII of the Periodic Table is always mediocre with regard to the amines and in the case of a catalyst, which is characteristic of cases, even poor; it generally fluctuates net, if such a complex compound is used from 20 to 50%. uses which as ligands at least one organic It has now surprisingly been shown that cal phosphite or a ligand whose tertiary donor atom oxygen, nitrogen or sulfur amines can be synthesized with the aid of the process according to the invention without the disadvantages mentioned above, and that a catalyst can be concentrated. The process leads to tertiary amines with over tration of 5 · 10 "* to 5 · 10" ³ mol / l total reaction high selectivity; adheres to the selectivity mixture. can reach up to 100% and always remains above 60%. ao The complex compounds used according to the invention consist of a Group VIII metal such as rhodium, iridium, platinum, palladium, ruthenium, Osmium, iron, cobalt or nickel and at least one of the following ligands: aliphatic, aromatic 35 tables and arylaliphatic phosphites, hexamethyl- The invention relates to a process for the production of phosphorotriamide, aliphatic and cyclic ethers of tertiary amines by reacting olefins such as dimethyl ether and diethyl ether, dioxane, dialkylamide Carbon monoxide, hydrogen and a secondary ether of glycol and acetylacetone, primary, secondary Amine under partial pressures of hydrogen and dear and tertiary aliphatic, aromatic and alides Carbon monoxide from 10 to 120 bar at a 3 <> cyclic amines, heterocyclic bases such as pyridine and a temperature of 60 to 250 ° C. for 10 min up to bipyridine, dialkyl and diary sulfides, acyclic ones 10 h in the presence of a coordination complex sulfide, sulfur-containing heterocycles and ligands Binding of a metal from group MU of the period with several donor atoms such as dimethyl sulfoxide, systems as a catalyst. Dimethyl glyoxime and amine oxides. The process is characterized in that such complex compounds are used according to known processes as ligands which are either produced in a separate process stage or produce and isolate at least one organic phosphite or they are formed in situ without a ligand, its donor -Atom oxygen, to be isolated beforehand, in that a corresponding nitrogen or sulfur is, and that a metal compound and the desired ligand are combined with a catalyst concentration of S- 10 ^β to S- Ό ³ 40, if necessary in excess. Mol / l total reaction mixture complies. For example, a carbonyl complex such as dichloro The principle of the production of amines starting from tetracarbonyldirhodium or an olefinic complex of the above starting materials is already known. such as dichlorotetraethylene dirhodium used. Various processes have been described in which the reaction is carried out in the presence of a solvent where catalysts of a certain type are used, which is an alcohol, a saturated one will. So describe the USA. Patents or aromatic hydrocarbon, an ether or 24 22 631 and 24 97 310 the use of metals can be a mixture of these solvents, of groups Vl, VII and VIII of the periodic table The method can be applied quite generally to all in the form of their salts or oxides. The reaction will employ linear or branched olefins. It is suitable carried out at increased pressure and causes a 5 »is particularly good for olefins, the 2 to 20 carbon average selectivity to amines. From the French material atoms contained in the molecule, such as ethylene, Pro-Patent 13 95 489 is the use of a Korn- pylen, the butenes, pentenes, hexenes, octene, dodecene plexes from tri- (hydrocarbon), phosphine and and octadecene. The olefins can be known individually or in cobalt carbonyl. The conversion of the mixture of oils used with one another, fine to amines, is about 50 "^ at a pressure of 55. Particularly suitable amines are secondary aliphatic 7 to 210 At and at a temperature of 100 to aromatic and cycloaliphatic amines, especially 250 ⁰ C. Finally, USA patent 35 13 200 describes the use of complex compounds, such as dimethylamine, diethylamine, dipropylgene, which are composed of a phosphine and optionally an amine, diitopropylamine, dibutylamine, diisobutylamine, specifically those containing 2 to 20 carbon atoms , Hydride of metals of group VIII of the periodic 60 DipentylamiUi dihexylamine, diheptylamine, dioctyl system and to which poly (heteroamine, Dethylhexyl) amine; Dittönylamih, Diphenyleyclo) amines can be added, in which amine, dibenzylamine, Butylcycloocrylamine; this amine at least one nitrogen atom at the same time two nuclei ne can be used individually or in a mixture with one another to form the polycyclic compound g heard. The implementation application is coming. wetting takes place at a temperature of 50 to 200 C ^ä "5 The reaction temperatures generally at Hegen and at a pressure of 5 to 300 At. A considerable amount of aldehyde is obtained and the selectivity is 60 to 250 ° C., usually 100 to 200 ° C. The reaction time is 10 min to 10 h, in this case too amines is very mediocre 5 h.