JPS5823376B2 - Method for producing N-vinyl substituted compounds - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing an N-vinyl substituted compound, and more specifically, the present invention relates to a method for producing an N-vinyl substituted compound. The present invention relates to a method for producing N-vinyl substituted compounds, which is characterized in that the corresponding N-vinyl substituted compounds are directly obtained.

Various N-vinyl substituted compounds are useful as polymeric monomers and as intermediate raw materials for synthetic organic compounds.

For example, N-vinylcarbazole polymers are extremely important as organic semiconductors.

Conventionally, the second method for synthesizing such N-vinyl compounds has been
Reppe (Reppe) by reaction of grade amine and acetylene
) law is famous (W, Reppe, Ann.

(Dan 1.128 (1956)).

However, since acetylene is used, there is a drawback that the reaction is dangerous.

In addition, as a method for synthesizing N-vinyl compounds other than the above, α
Or dehydration reaction of β-oxyethyl derivatives, dealcoholization reaction of α-alkoxyethyl derivatives.

De/SO hydrogenation reactions of α- or β-ethyl halide derivatives are known (Polymer Science Society of Japan Line).

Polymer Experiments 2, “Monomer I”, Kyoritsu Detatsu Publishing 340.
(1976), it has drawbacks such as requiring several reaction steps for the synthesis of intermediate raw materials.

In this respect, a method for directly synthesizing N-vinyl substituted compounds by reacting nitrogen compounds such as secondary amines with olefins is desired, but no satisfactory results have been obtained so far.

For example, a related reaction is the vinylation of alkylamines using palladium and catalysts, but this has many problems in terms of catalyst efficiency and selectivity.

(P, M, Maitlis. The Organ
ic Chemistry of Palladium
.

Vol II, P 157, Academic P
ress, 1971).

In addition, there is a vinyl group exchange reaction with a secondary amine using vinyl acetate or vinyl ether, but it uses a mercury compound as a catalyst and it is difficult to introduce a vinyl group with a functional group (
The above ``monomer■''.

P341).

The present inventors have previously discovered that alkenylbenzene can be obtained in good yield by reacting benzene with an olefin compound in the presence of carbon monoxide using a rhodium carbonyl complex as a catalyst, and disclosed in JP-A-55-115829 (No. Publication Sanma) Also, in the reaction between fucins and olefin compounds,
It has been found that alkenylfuran 7 can be obtained in good yield (see Japanese Patent Application No. 133200/1982).

The present inventors further carried out an intensive search from a wide range of applicable compounds, and found that N-vinyl-substituted compounds were found to be good catalysts directly from the reaction between the secondary amines and olefin compounds. found that it could be obtained in high yield,
The present invention has now been completed.

The present invention uses a rhodium complex mainly composed of rhodium carbonyl as a catalyst, and reacts nitrogen compounds including secondary amines with an olefin compound in the presence of carbon monoxide.
It relates to a method for obtaining the corresponding N-vinyl substituted compounds.

That is, in the present invention, using a rhodium carbonyl complex as a catalyst, in the presence of carbon monoxide, the general formula: (wherein R1 and R
2 independently represents an alkyl group or an aryl group, or R1 and R2 are combined (in the formula, R3, R4, R7, and R8 independently represent a hydrogen atom, a halogen atom, or an alkyl group, and R5 and R6 are independently represents a hydrogen atom or an alkyl group.

) to form. ) and the general formula: %Formula% (wherein, R9 represents a hydrogen atom or an alkoxycarbonyl group).

) is reacted with an olefin compound represented by the general formula: (wherein R1, R2 and R9 are the same as above).

) provides a method for producing an N-vinyl substituted compound, which is characterized by obtaining an N-vinyl substituted compound represented by

The nitrogen compounds used in the present invention include imines such as indole and carbazole, imides such as phthalic acid imide, or nuclear substituted derivatives thereof, diphenylamine, and N-methylaniline.

Refers to secondary amines such as diethylamine.

On the other hand, olefin compounds are ethylene and acrylic esters.

The present invention directly produces N- from these nitrogen compounds and olefins.
Although vinyl-substituted compounds are produced, the resulting product depends on the combination of raw materials used.

For example, when ethylene is used, an N-vinyl compound is obtained, and when methyl acrylate is used, an N-(2-(methoxycarboni/L/)vinyl) compound is obtained.

For example, using Rh, (co)1□ as a catalyst for the reaction of carbazole and ethylene, under pressure of carbon monoxide (25
kg/CrIt) at 200° C., N-vinylcarbazole is obtained in a yield of 64% (based on the carbazole used).

Further, N-vinylindole is obtained by reaction of indole and ethylene.

Also, when methyl acrylate and indole are reacted, 1-
(2-(methoxycarbonyl)vinyl coindole is 6
Obtained with a yield of 2%.

At this time, the same amount of methyl propionate, which is a reduced form of the raw material, is produced.

This is because 1 mol of hydrogen molecules produced during production of the target product reduces methyl acrylate.

As shown in the above examples, one of the present invention is Rh4(Co)1□
It uses rhodium carbonyl as a catalyst, but in addition to this, Rha(co)t6 and Rh2(CO)4C
Carbonyl complexes such as 12°Rh(CO)2(acac) as well as Rh2(1,5-cyclooctadiene)2
It may also be a rhodium complex such as c4 that can be converted into rhodium carbonyls in the presence of carbon monoxide.

In the present invention, one important feature of the present invention is that the reaction can proceed easily by carrying out the reaction in the presence of the -acid f-arsenic carbon. The pressure required for suppressing decomposition and used in one reaction is not limited, but usually 1 to 100 kg/criY, preferably 20 to 30 to 9/ffl is sufficient.

The solvent used in the present invention is benzene.

Baraxylene, tetrahydrofuran, dioxane.

Examples include ethanol, hexane, etc.

Among the nitrogen compounds mentioned above, those that are liquid under reaction conditions, such as N-methylaniline and diethylamine.

It can also be used itself as a solvent.

The reaction temperature varies depending on the reagents used, but is usually 150°C.
-300°C, preferably 200°-250°C is suitable.

The appropriate reaction time is usually 2 to 10 hours, preferably 4 to 8 hours.

The compounds obtained by the present invention can be used as agricultural chemicals and pharmaceuticals.
It is also useful as an intermediate raw material.

In particular, N-vinylcarbazole is important as an organic semiconductor raw material as described above.

The present invention will be explained below by way of examples.

Example 1 Carbazole (0,84!11) as Rh, (Co)1□
(0,019 g) and benzene (23,49) in a stainless steel autoclave with an internal volume of 100 m1, as well as ethylene (20 kg/d) and carbon monoxide (25 k
g/i) were sequentially charged and allowed to react at 200° C. for 7 hours while shaking.

After cooling, the reaction mixture was taken out and analyzed using a gas chromatograph (
(hereinafter referred to as GC), N-vinylcarbazole was 0.62.9% (yield 64% based on the carbazole used).
The generation of was confirmed.

The product was isolated by silica column chromatography,
This was confirmed by comparing the IR and NMR spectra with the standard product.

Examples 2-4 Reaction and analysis were carried out in exactly the same manner as in Example 1 except that carbazole (1.67 g) and the reaction solvent shown in Table 1 (0.3 mol) were used to investigate the influence of the reaction solvent. .

The results are shown in Table 1. Example 5 Substituting indole (o, ss5.9) for carbazole 1
The reaction was carried out in the same manner as in Example 1 except that the reaction source degree was set at 220°.

The obtained reaction solution was concentrated under reduced pressure and then separated by silica column chromatography.

0.2 from the part eluted with benzene-hexane (1/)
429C consumed indole standard yield 65%) N-
Obtained vinyl indole.

In addition. GC analysis of the reaction solution confirmed 0.2759 unreacted indole.

Example 6 Indole (0,58
Fl), methyl acrylate (4.48 g).

p-xylene (31,8 g) and Rh6(co)t.

(o, oiB) was added, and carbon monoxide (25 was filled with 0) and reacted at 220°C for 7 hours with shaking.

The resulting reddish-brown reaction solution was concentrated under reduced pressure and then separated using silica column chromatography.

, 100 benzene, 0.621 of 1-(2-(methoxycarbonyl)vinyl)-indole (indole standard yield 62%) from the part eluted with benzene-methylene chloride (/1)
was obtained as colorless crystals.

The structure of this product was confirmed by comparison of IR spectrum, NMR spectrum and mass spectrum, and analysis results.

[Physical properties]

m, p,: 93-95°C Elemental analysis values: C71, 61%, H5, 50%.

N6.90%, Calculated value as C1□H1, NO2 C71, 63%.

H5, 51%, N6.96% Mass spectrum: M+201 (calculated value 201) NMR (
(in deuterated chloroform): δ (ppm) 3.75 (s, 3
H), 5.91 (d, j = 14Hz.

IH), 8.24 (d, j = 14Hz, IH)
6.68 (d, j=4Hz, IH), 7.3
1 (d, j = 4Hz, IH), 7.1-7.7 (m, 4
H) Example 7 Carbazole (0,845,9) and methyl acrylate (
The reaction of 4, 34, 9) was carried out in exactly the same manner as in Example 6 using benzene (23, 4, !9) as a solvent.

The obtained orange-brown reaction solution was concentrated under reduced pressure and then separated by silica column chromatography.

1-(2
-(Methoxycarbonyl)vinyl seacarbazole (yield 44% based on carbazole) was obtained as colorless crystals.

[Physical properties]

m, p,: 120.5-121°C Elemental analysis value:
C76, 51%, H5, 18%, N5.53%, C16
Calculated values as H13NO2: C76,48%, H5,21%, N5.57%.

Mass spectrum: M 251 (calculated value 251) NMR
(in deuterated chloroform) δ (ppm): 3.92 (s
, 3H), 6.31 (d, j=12Hz.

IH), 8.50 (d, j = 12Hz, IH
), 7.2-8.4 (m, 8H) Example 8 Phthalic acid imide (1,437 g) and methyl acrylate (
4,:l) was carried out in exactly the same manner as in Example 6 using benzene (23.4 g) as a solvent.

The resulting pale orange solution was concentrated under reduced pressure and then separated using silica column chromatography.

Colorless crystals of N-C2-(methoxycarbonyl)vinylthiphthalimide (0.18 g, yield 8% based on phthalic acid imide) were obtained from the portion eluted with benzene-chloride, 42 methylene (/1 to /1).
I got it.

[Physical properties]

m, p,: 139-141°C Mass spectrum: M+231 (calculated value 231) NMR (
(in deuterated chloroform) δ (ppm): 3.79 (s,
3H), 6.93 (d, j = 14Hz.

IH), 7.92 (d, j2 14Hz, IH),
7.7-8.0 (m, 4H) Elemental analysis values: C62, 42%, H3, 97%, N5.9
3%; Calculated value as C, 2H0NO, C62, 34%
, H3, 92%, N6.06%.

Example 9 The reaction between diphenylamine (0,845 g) and methyl acrylate (4.4 g) was carried out in exactly the same manner as in Example 6 using benzene (23.4 g) as a solvent.

The obtained pale orange-red solution was concentrated under reduced pressure and then separated by silica column chromatography.

Benzene-chloride, 43 N-(2-
(methoxycarbonyl)vinylcydiphenylamine (
0.28 g (yield 24% based on diphenylamine) was obtained as a colorless oil.

[Physical properties]

Mass spectrum: M+235 (calculated value 235) NM
R (in deuterated chloroform) δ (ppm): 3.70
(s -5H), 4.85 (d, 13Hz, IH),
8.17 (d.

j-=13Hz, IH), 7.0-7.6 (m,
10H) Example 1O N-methylaniline (2,11,9) and methyl acrylate (8,6(1) to Rh, (CO)1□(0,020,
9) and benzene (5077Il) together with 200TILl
In addition to the stainless steel autoclave, carbon monoxide (30
kii) and heated at 220°C for 6 hours while shaking.

The obtained reddish-brown solution was concentrated under reduced pressure and then separated by silica column chromatography.

13 The target product N-(2-(methoxycarbonyl)
Vinylcou N-methylaniline is 1. (Hi' (N-methylaniline standard yield 26%) was obtained.

[Physical properties]

Mass spectrum: M 191 (calculated value 191) NMR
(in deuterated chloroform) δ '3.22 ((ppI[
l) 's, 3H), 3.68 (s, 3H), 4.92 (d
, j = 13Hz, IH), 7.91 (d, j = 1
3Hz, IH), 7.0-7.5 (m, 5H) Example 11 Diethylamine (3,6:l) and methyl acrylate (4
, :l) and benzene (23,4,9) to R114(CO
)t□ (0,019 g) was added to a 100 TL stainless steel autoclave, filled with -carbon oxide (5 kg/=), and heated at 200°C for 6 hours with shaking.

The resulting red solution was concentrated under reduced pressure and then separated using silica column chromatography.

The target product N- as a colorless oil was obtained from the part eluted with benzene.
[0.899 of 2-(methoxycarbonyl)vinylcydiethylamine (yield 10% based on diethylamine) was obtained.

[Physical properties]

Mass spectrum: M 157 (calculated value 157) NMR
(in deuterated chloroform) δ; 3.78 ((p)s, 3H), 1.16 (t, j-=6Hz, 6H).

3.26 q, j = 6Hz, LH), 4.
56 (d, j2 13Hz, IH), 7.48 (d
, j=13Hz, IH).

Claims (1)

[Claims] 1 Using a rhodium carbonyl complex as a catalyst and in the presence of carbon monoxide, the general formula: (wherein R1 and R2 independently represent an alkyl group or an aryl group, or R1 and R2 are bonded (in the formula,
R3, R4, R7 and R8 independently represent a hydrogen atom, a halogen atom or an alkyl group, and R5 and R6 independently represent a hydrogen atom or an alkyl group. ) to form. ) is reacted with an olefin compound represented by the general formula: % formula % (wherein R9 represents a hydrogen atom or an alkoxycarbonyl group), is the same as above.) 1. A method for producing an N-vinyl substituted compound, which comprises obtaining an N-vinyl substituted compound represented by: