KR880002620B1 - Light catalyzed process for preparing amines - Google Patents

Abstract

Prepn. of aromatic and aliphatic amines comprises reacting NH3 or a primary or secondary amine with an olefin in the presence of a light of wavelength over 1600 ∦ and a photocatalyst which is stable to UV light, and adding N-H bond of the amine or NH3 to the double bond of the olefin. The reaction is carried out in a reactor vessel having amorphous silica glass walls. The amines are widely used as intermediates in prodn. of rubber products, pharmaceuticals, insecticides, dyestuffs and textile finishing agents.

Description

Method for preparing amine by photocatalytic method

The present invention relates to a process for preparing aliphatic and aromatic amines from olefins and ammonia or primary or secondary amines, in particular aliphatic, cycloaliphatic from olefins and ammonia or primary or secondary amines under the catalytic use of actinic light. , Heterocyclic aliphatic, or aromatic amines. This application is a continuation of US Patent Application No. 259,731 (filed May 1, 1981), which is a continuous application of US Patent Application No. 143,989 (filed April 28, 1980, now abandoned). In the prior art, as a method for preparing an amine, a nitrile, a nitro compound or the like is reduced, or a hydroxyl group in alcohol, an aryl chloride or chloro or bromo group in bromide, oxygen in carbonyl group of aldehyde or ketone, or ether There has been a method of substituting amino groups for other functional groups such as alkoxy groups. The direct synthesis of amines from olefins does not require such functional group containing intermediate compounds and simplifies the separation and purification of the desired amines.

U.S. Patent No. 2,772,271 describes that the reaction of amines with α-olefins in the presence of peroxides or light results in the addition of olefins to the α-carbon atoms of the amines. Similarly, U.S. Patent No. 3,492,353 describes a similar reaction performed using trimethylamine as an amine, either under the presence of a pre-radical catalyst or under actinic irradiation with a quartz mercury lamp (radiated above 2240 Hz), as a result of this reaction. The olefin molecule is added to the α-carbon atom to form amino nitrogen. The following literature describes a process for preparing benzene by reacting primary and secondary amines with 1, 2- and 1,3-minerals. See, for example, Angew. Chem., Int'l Ed., 13, 341 (1974)], in which the photochemical addition of dialkylamines to stilbenes (activated olefins) results in the addition of N, N dialkyl-1, 2- Diphenylethylamine is formed but yields are low (15-20%) because of the use of a technique with a minimum wavelength of 2900 kHz. FD JACS 99, 7991 (1977) by Lewis and T. Ho and J. Chem. By M. Kawanisi and K. Matsunaga. Soc. Chem. Commun. 313 (1971).

US Pat. No. 2,749,297 describes a process for producing aniline, toluidine and xyldine and hydrogen by reacting ammonia with benzene, toluene or xylene under the influence of actinic irradiation or non-dividing discharge, respectively. It is not mentioned. The present invention is characterized by adding NH bonds of amines or ammonia to double bonds of olefins by reacting primary or secondary amines or ammonia with olefins in the presence of light with a wavelength of 1600 to 2200 ,, or light and photocatalyst with a wavelength of 1600 Å or more. The present invention relates to a method for producing aliphatic and aromatic amines. The method of the present invention can be described by the following scheme.

(Suprasil

Heraeus Amersil 제품)과 코닝 #7940(Corning 7940, Corning Glass Company 제품)이란 상품명으로 시판되고 있다.This method can be performed with or without a photocatalyst, depending on the actinic radiation source used. If no suitable photocatalyst is present, the light source should have an output in the spectral region of about 2200 Hz to about 1600 Hz. Since the reactors and lamps used in this method usually consist of a vessel with a conventional quartz glass wall for the passage of actinic light, in practice the lower-wavelength end is always light transmission of the usual quartz glass. cut-off) (around 1800 µs). However, we have found that the use of amorphous silica or synthetic silica glass as the vessel wall or lamp glass of the apparatus used in this method is beneficial because it transmits ultraviolet radiation of shorter wavelengths (blocking around 1600 Hz) than conventional quartz glass. . Glass made of this synthetic silica is suprasyl

(Suprasil

Heraeus Amersil) and Corning # 7940 (Corning 7940, Corning Glass Company).

Representative lamps emitting from 1600 to 2200 Hz include deuterium lamps, low pressure mercury-argon lamps and high energy xenon flash lamps, among which high energy xenon flash lamps are particularly effective due to their high energy intensity and large output powers at 1800 to 200 Hz. effective. This is only an example and it is not the only one that can be used. Lamps that transmit light with wavelengths above this range are effective only in the presence of a photocatalyst: In addition, low energy flashlights that peak at about 4000 Hz require a photocatalyst to produce a suitable yield in the reaction. As used herein, "photocatalyst" refers to a substance that, when added to a reactant, causes a desired reaction to occur at a significantly increased rate under actinic light effects. Although not wishing to be bound by any theory, photocatalysts may use mercury or transition metal coordination compounds, or mercury, which may form complexes with light-absorbing organic compounds, olefins, and amine reactants and make them more sensitive to reactions under chemiluminescence effects. have.

Useful organic photosensitizers include ketones, aromatic hydrocarbons, alcohol organometallic compounds, heterocyclic amines, organic dyes, sulfur compounds, and organic derivatives of Group VA elements, and the following organic photosensitizers are useful in the present invention. : Acetone, 2-butanone, 2-pentanone, 3-pentanone, 4-heptanone, diisopropyl ketone, acetophenone, isobutyrophenone, propiophenone, benzophenone, 3-hydroxy-2- Butanone, 2, 4-pentanedione, benzene, m-xylene, diacetone alcohol, pyridine, 2, 2'-diethoxyacetophenone, triphenylphosphine, triphenylarcin, triphenylbismutin, triphenyl Stybin, tributylpostin and 8-hydroxyquinoline, of which preferred are acetone, 2-butanone and 2, 4-pentanedione.

Suitable transition metal complexes are coordination compounds of rhodium, ruthenium, iron and molybdenum, for example: hydromocarbonyltris (triphenylphosphine) rhodium (I), chlorotris (triphenylphosphine) rhodium (I) , Dichlorobis (dimethylglyoxymato) rhodium (III), dichlorobis (phenylmethylglyoxymato) rhodium (III), methyl aquabis (dimethylglyoxymato) rhodium (III), chlorotriphenylphosphine bis (dimethyl Glyoxymato) rhodium (III), dichlorotetrakis (isoquinolino) rhodium (III) chloride, dichlorotris (triphenylphosphine) ruthenium (II), hexamolybdenum dodeca chloride, general formula Mo ₆ Cl ₁₂ , [ Mo ₆ Cl ₈ ] Cl ₄ L _2, where L is a ligand that may be substituted with an amino reactant and may be an amino reactant (eg, (CH ₃ ) ₂ NH or NH ₃ ) itself) Cluster) Compound and Group VIII Metal Carbonyl, Preferred of the The transition metal photocatalyst is dichlorotris (triphenylphosphine) ruthenium (II), chlorotris (triphenylphosphine) rhodium (I), general formula [Mo ₆ Cl ₈ ] Cl ₄ L ₂ , wherein L is as described above. ) Molybdenum (II) cluster compound and Fe (CO) ₅ .

The photocatalysts may be used alone or in combination to increase conversion and yield. Especially preferred are mixtures of Fe (CO) ₅ with one or more of the following compounds. Tri (n-butyl) phosphine, tri (n-propyl) phosphine, triethylphosphite, diethylphenylphosphine, diphenylchlorophosphine, bis (1,2-diphenylphosphino) ethane and 2 , 4-pentanedione. The organic photocatalyst may be added in a catalytically effective amount relative to the amine or ammonia reactant and the preferred range is below the solubility limit of the organic photocatalyst. Transition metal photocatalysts can be added in effective amounts but are typically used as solubility limits in ammonia or amine reactants.

Mercury is usually used as a vapor phase catalyst prepared by passing an inert carrier gas (such as helium) through an element of mercury maintained at a vaporization temperature (200 ° C). If necessary, elemental mercury droplets may be used in the absence of a carrier. The mercury catalyst is used in an amount more than sufficient to exhibit catalytic activity. The maximum concentration of mercury used with an inert carrier includes the amount of mercury vapor obtained by the flowing gas at the saturated vapor pressure of mercury. Suitable reactants containing N-H bonds are ammonia and various primary and secondary amines. Examples of such amines are: methylamine, dimethylamine, ethylamine, diethylamine, n-propylamine, isopropylamine, di (n-propyl) amine, di (isopropyl) amine, n-butylamine , Di (n-butyl) amine, secondary-butylamine, di (secondary-butyl) amine, isobutylamine, di (isobutyl) amine, pentyl and higher alkylamine; Alicyclic amines such as cyclohexylamine; Aromatic amines such as aniline, N-alkylaniline, diphenylamine, naphthylamine and toluidine; Heterocyclic amines such as pyrrolidine, morpholine and piperidine; Substituted amines such as alkanolamines; And polyamines such as ethylenediamine and 1, 6-hexadiamine.

Preferred among the NH-containing reactants are ammonia and mono- and di-alkyl (C ₁ -C ₆ ) amines which are readily available for purchase. Particularly preferred NH containing reactants are ammonia. Olefin compounds suitable for the present invention have one or more non-aromatic carbon-carbon double bonds (internal and / or terminal), examples of such compounds are: ethylene, propylene, 1-butene, 2-butene, isobutyl Ene, 1-pentene, 2-pentene, 3-methyl-1-butene, 2-methyl-1-butene, 2-methyl-2-butene, various possible hexenes, higher alkenes (e.g. dodekenes), cyclobutene, Cyclopentene, cyclohexene, cycloheptene, stilbene, styrene, α-methylstyrene, α, α-dimethylstyrene, cyclopentadiene, cyclohexadiene, cyclooctadiene, butadiene, 2-methyl-1,3-butadiene, 2-chloro-1,3-butadiene, cyclododecatriene, acrylonitrile vinyl chloride, methyl vinyl ether, allyl alcohol and furan.

Double bonds close to groups capable of stabilizing pre-radicals can be activated and they generally react much more easily than inactive double bonds. Preferred olefins for the purposes of the present invention are inactivated alkenes having 2 to 8 carbon atoms with terminal double bonds which are easy to purchase. N-H containing reactants and olefins may be optionally substituted with various groups (e.g., -OH, -halide, -CN) provided that these groups do not interfere with the reaction. Typical temperatures used to carry out the invention are -10 to 40 ° C, although other temperatures may be used, with -10 to 10 ° C being preferred. Using lower temperatures increases the solubility of gaseous olefins (eg ethylene) in liquid ammonia or amines. The molar ratio of amine to olefin as ammonia or starting material is from 1: 1 to 20: 1, preferably from 5: 1 to 15: 1. The reaction of the present invention is preferably carried out in the liquid phase, but may also be carried out in the gas phase or solid phase. When performed in gas phase, certain solid photocatalysts may be banned due to their low vapor pressure.

EXAMPLE

The following examples illustrate the process of the present invention which is carried out in an apparatus that can be used in a continuous process in liquid or gas phase using known reactant and photocatalyst introduction methods and separation of products from starting materials.

Example 1

18.2 moles of ammonia are charged to a reactor system consisting of a 1 L stainless steel reservoir, a quartz reactor for irradiating the solution to the solution and a circulating pump. An ultraviolet light source is installed outside the quartz reactor. The reactor and light source are placed in a reflective stainless steel cylinder. Ethylene is then charged until the pressure reaches 260 psig and 2.3 moles of ethylene are dissolved in ammonia. The solution is circulated for about 1.5 hours before the lamp is turned on to properly mix and the reaction mixture is cooled to 7-8 ° C. No reaction is observed at this time. The cyclic autogenous liquid reaction mixture is then exposed to an ultraviolet lamp for the time given in Table 1. The result of measuring the final mixture by gas chromatography is described in the table. The conversion is for ethylene and the yield is for mixed mono-, di- and tri-ethylamine. Using the high-energy xenon flashlamp in Table 1, discharge 25 joules through a 10 cm path through a 1 mm inner diameter: the spectral output is in the 300 kHz range.

TABLE 1

에서 피크를 나타내는 저에너지 크세논 플래쉬램프를 사용하면 수율이 낮다는 것을 쉽게 알 수 있다.From Table 1, 25joules are discharged through a 10cm pass through a mercury lamp and an inner diameter of 13mm with no output below 2200 2, and the spectral output is 4000.

It is easy to see that the yield is low by using a low energy xenon flash lamp that shows a peak at.

Example 2

18.2 moles of ammonia and 0.9 moles of acetone are charged to the reactor system described in Example 1 and ethylene is added to the system to dissolve 2.3 moles of the ammonia-acetone solution. After the solution has been circulated for 1.5 hours, the deuterium lamp is turned on and the solution is exposed for 4 hours. Analysis of the final mixture by gas chromatography showed ethylene conversion of 27.9% and yield of mono-, di- and tri-ethylamine 72.1%.

Example 3

A mixture consisting of 18.2 moles of ammonia, 1.82 moles of 1-butene and 0.9 moles of acetone is charged to the reactor system described in Example 1 except that a 550-watt mercury lamp is used as the light source. The high pressure liquid mixture is circulated at 8 ° C. for 4 hours. Analysis by gas chromatography and mass spectrometry showed that the conversion to N-ethyl-nbutylamine was 7.0%. If no acetone is used, no product is observed.

Example 4

A mixture consisting of 17.0 moles of ammonia, 1.72 moles of 1-octene and 0.88 moles of acetone is charged to the reactor system described in Example 1 and circulated at 8 ° C. for 5 hours. Use 550-w mercury lamp as uv light source. Distillation to collect 2.9g octylamine as a product at 180 ℃ and confirmed by NMR and confirmed by titrimetry. If no acetone is used, no product is observed.

Example 5

A mixture of 8.68 g mole ethylamine, 1.43 mole 1-butene and 0.7 mole methyl ethyl ketone is charged to the reactor system described in Example 1. The reaction mixture was circulated for 4 hours at 8 ° C. using a 550-w mercury lamp as a light source. As a result, the conversion of 1-butene was 5.0% and the yield to N-ethyl-n-butylamine was 100%.

Example 6

A mixture of 5.0 moles of n-butylamine, 0.5 moles of acetone and 0.84 moles of ethylene is charged to the reactor system described in Example 1. The reaction mixture was circulated for 4 hours at 8 ° C. using a 550-watt mercury lamp as a light source. The conversion of ethylene was 12.0% and the yield to N-ethyl-n-butylamine was 100%.

Example 7

A mixture of 7.60 moles of dimethylamine, 1.15 moles of ethylene and 0.0023 moles of Mo ₆ Cl ₁₂ is charged to the reactor system described in Example 1. The reaction mixture was circulated for 4 hours at 8 ° C. using a 550-watt mercury lamp as a light source. The conversion of ethylene was 10%, and the combined yield of dimethylethylamine, diethylmethylamine and triethylamine was about 100%. It was.

Example 8

A mixture of 4.04 moles of n-butylamine, 0.221 moles of Fe (CO) ₅ and 0.221 moles of triethyl phosphite was charged to the reactor system described in Example 1 and pressurized to 250 psig with ethylene at 35 ° C. Let's do it. The light source uses a 550-watt high-pressure mercury ultraviolet lamp. The mixture is circulated for 4 hours under constant irradiation. The product was analyzed and the conversion from n-butylamine to n-ethyl-n-butylamine was 15.5%.

Example 9

시간 동안 또는 용액온도가 7 내지 8℃에 도달할때까지 순환시킨다. 램프를 켜고 용액을 4시간 조사시킨다. 반응기 및 조사용 램프에 있어 무정형 실리카유리의 영향을 알기위해, 상술한 과정을 사용하여 8회 시험한 결과를 다음표에 기술하였다. 8회 시험중 4회에서는 반응기 벽으로 통상 석영 유리를 사용한 반면 나머지 4회에서는 반응기 벽으로서 무정형 실리카 유리(Suprasil)

를 사용하였다.18.2 moles of ammonia and 0.18 moles of ammonium chloride (NH ₄ Cl) are charged to a 1 l circulation system equipped with a circulation pump, a cooling coil and a cylindrical glass reactor. An ultraviolet lamp is placed near the reactor and the reactor and lamp are placed in a reflective stainless steel cylinder. Ethylene is charged into the system until the pressure reaches 250 psig. The resulting solution

Circulate for hours or until solution temperature reaches 7-8 ° C. Turn on the lamp and irradiate the solution for 4 hours. In order to know the effect of amorphous silica glass on the reactor and the lamp for irradiation, the results of eight tests using the above procedure are described in the following table. In four of the eight trials, quartz glass was typically used as the reactor wall, while in the other four, amorphous silica glass (Suprasil) was used as the reactor wall.

Was used.

로 싼 램프를 사용하였다. 표에서 전환율 %는, 각 경우 생성물인 에틸아민을 상응하는 하이드로클로라이드로서 수득하였기 때문에, 존재하는 염화암모늄의 양을 기준한 것이다. 수율은 실질적으로 정량적이다.In these two (four times per test) trials, two of them used an irradiation lamp wrapped with ordinary quartz glass, and the other two were amorphous silica glass (Suprasil).

Cheap lamps were used. The% conversion in the table is based on the amount of ammonium chloride present since in each case the product ethylamine was obtained as the corresponding hydrochloride. The yield is substantially quantitative.

TABLE 2

Conversion to ethylamine

a. 550 watt high pressure mercury lamp

b. Low intensity xenon flash lamp

Example 10

Simultaneous exposure of gaseous ammonia, ethylene, helium and mercury vapors to ultraviolet light in a single-pass reactor system consisting of a flow regulator, a mercury-reflux pot made of stainless steel and a quartz reactor chamber Let's do it. The helium stream is first passed through an element of mercury heated to about 200 ° C. and immediately He / Hg vapor is mixed with a mixture of ethylene and ammonia (1: 1 volume ratio) and introduced into the reactor chamber. The reactor chamber is irradiated with a low pressure mercury lamp installed outside the reactor. The exhaust gas was collected and analyzed and the product was identified to be 85-98% pure ethylamine.

Claims (13)

NH bonds of amines or ammonia are added to double bonds of olefins by reacting primary or secondary amines or ammonia with olefins in the presence of light with a wavelength of 1600 to 2200 Å, or light and photocatalyst with a wavelength of 1600 Å or more. The method of manufacturing an amine by this. The process of claim 1 wherein the reaction is carried out in a reaction vessel having an amorphous silica glass wall. The method of claim 1 wherein the photocatalyst is mercury, a light absorbing organic compound, a transition metal complex or a mixture thereof. The method of claim 3, wherein the organic compound is a ketone, an aromatic hydrocarbon, an alcohol, an organometallic compound, a heterocyclic amine, an organic dye, a sulfur compound or an organic derivative of a Group VA element. The method of claim 3 wherein the photocatalyst is a coordination compound of rhodium, ruthenium, iron or molybdenum. The photocatalyst of claim 3, wherein the photocatalyst is dichlorotris (triphenylphosphine) ruthenium (II), chlorotris (triphenylphosphine) rhodium (I), Mo ₆ Cl ₁₂ , general formula [Mo ₆ Cl ₈ ] Cl ₄ L A molybdenum cluster composition of ₂ , wherein L is a ligand that can be substituted with an amino reactant, or Fe (CO) ₅ . The process of claim 3 wherein the photocatalyst is a mixture of Fe (CO) ₅ ) and one or more of the following compounds: tri (n-butyl) phosphine, tri (n-propyl) phosphine, triethylphosphite, di Ethylphenylphosphine, diphenylchlorophosphine and bis (1,2-di-phenylphosphino) ethane. The process of claim 1 wherein the N—H containing reactant is ammonia or a mono or di-alkylamine in which the alkyl group contains 1 to 6 carbons. The method of claim 8, wherein the olefin is an alkene having 2 to 18 carbon atoms. 10. The method of claim 9, wherein the alkene contains a terminal double bond and 2 to 8 carbons. The method of claim 10, wherein the photocatalyst is acetone, 2-butanone or 2,4-pentanedione. The photocatalyst of claim 10, wherein the photocatalyst is dichlorotris (triphenylphosphine) ruthenium (II), chlorotris (triphenylphosphine) rhodium (I) Mo ₆ Cl ₁₂ [Mo ₆ Cl ₈ ] Cl ₄ L ₂ , where L Is a ligand which may be substituted with an amino reactant) or Fe (CO) ₅ . The process according to claim 11 or 12, wherein the reaction is carried out in a reaction vessel having an amorphous silica glass wall.