JPS58225035A - Production of 1-phenyl-2,2-dialkoxypropane - Google Patents

Abstract

PURPOSE:3-Phenylpropylene, which is readily available, is used as a starting compound to effect the reaction with an alkyl nitrite in the presence of an alcohol and a Pd catalyst to produce the titled compound used as an intermediate of agricultural chemicals, medicines or the like. CONSTITUTION:A 3-phenylpropylene which may bear substituents on its benzene ring of the formula (X, Y, Z is H, hydroxyl, halogen, nitro, amino or alkyl, where two of them incorporate with 1 or 2 oxygen atoms to form a heterocyclic ring), which is obtained by extracting a vegetable oil or reaction of benzene or substituted benzene with an allyl halide, is made to react with an alkyl nitrite in an alcohol, preferably the same alcohol as that of the nitrite ester, in the presence of a catalyst of Pd, preferably palladium chloride, to give the titled compound. EFFECT:Unreacting raw materials and the alcohol can be recycled and the NO gas liberated by the reaction is utilized for a production of a nitrite ester.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing 1-phenyl-2,2-dialkoxypropanes.

L-phenyl-2,2-dialkoxypropanes are compounds used as intermediate raw materials for various agricultural chemicals and pharmaceuticals, for example, as an intermediate for producing L-α-methyldopa. A method of manufacturing by reacting a phenylacetylene compound with 2 moles of alcohol is used. However, this production method has problems such as difficulty in obtaining the phenylacetylene compound used as a raw material.

The present invention utilizes l-phenyl-2 using readily available raw materials.
, 2-dialkoxypropanes.

The present invention provides 3-benzene rings which may have substituents.
Process 9 for producing l-phenyl-2,2-dialkoxypropanes is characterized in that phenylpropylene is reacted with an alkyl nitrite ester in the presence of an alcoholic palladium salt catalyst.

Next, the present invention will be explained in detail.

One of the raw materials of the present invention is 3-phenylpropylene, and the benzene ring of this 3-phenylpropylene may have a substituent. Examples of the substituent include a hydroxyl group, a halogen atom, a nitro group, an amino group, a lower alkyl group having up to 6 carbon atoms, and a lower alkoxy group having up to 6 carbon atoms. These substituents can be attached to the benzene ring in a total number of up to three. Therefore, the 3-phenylpropylene used in the present invention can be represented by the following formula (I).

CH2-CH=CH2,l (X, Y, and Z are hydrogen atoms and hydroxyl groups, respectively.

halogen atom, nitro group, amino group, lower alkyl group,
A substituent selected from the group consisting of lower alkoxy groups,
, Y, and Z may be the same or different; alternatively, 5 to 7 in which any two of x, y, and z contain 1 to 2 oxygen atoms together with a part of the benzene ring. The 3-phenylpropylenes represented by the above formula (I) can be extracted from naturally occurring vegetable oils or combined with the corresponding benzene or substituted benzene compound and halogen. It can be easily obtained by reaction with allyl compound (CH2=CH-CH2Br, etc.).

Another raw material of the present invention is an alkyl nitrite ester, which can be represented by formula (U).

RONO(n) (R is an aliphatic, aromatic, or alicyclic saturated or unsaturated alkyl group, preferably an alkyl group having 1 to 10 carbon atoms or a benzyl group).

In the above formula (n), R is preferably an aliphatic group such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, or an aromatic group such as benzyl. , especially saturated aliphatic alkyl groups having 1 to 4 carbon atoms, i.e. methyl, ethyl, n-propyl, isopropyl, n-butyl, 5e
Preferably, it is c-butyl.

Therefore, the reaction on which the production method of the present invention is based can be expressed as follows.

■ R As can be seen from the reaction formula above, it is necessary to use 2 or more moles of nitrite alkyl ester per mole of 3-phenylpropylene, and in actual reactions, it is necessary to use at least 2 mole of nitrite per mole of 3-phenylpropylene. 2 to 5 mol, preferably 2.1 to 3.5 mol.

The above reaction advantageously proceeds in the presence of a catalyst of alcohol and palladium salt. Examples of the alcohol used here include alkyl groups having 1 to 10 carbon atoms such as methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol, pentyl alcohol, hexyl alcohol, heptyl alcohol, octyl alcohol, nonyl alcohol, decyl alcohol, and benzyl alcohol. Alternatively, an alcohol having benzyl groups is preferable. In addition, using an alcohol that has the same alkyl group as the alkyl group of the nitrite alkyl ester used in the reaction has the advantage of making it easier to recover and reuse the alcohol from the reaction solution, so it is recommended to select such an alcohol. Preferred such alcohols are usually used in an amount of 1-1 per mole of 3-phenylpropylene used.
0 times used.

In addition, since the above alcohol also acts as a reaction solvent,
There is no particular need to use other solvents, but other solvents can be used if desired. Such a solvent is not particularly limited as long as it is substantially inert to the reaction utilized in the present invention, but examples of suitable solvents include:
Lower fatty acid esters such as ethyl acetate and butyl acetate, ethers such as dioxane, dibutyl ether and tetrahydrofuran, aromatic hydrocarbons such as benzene, toluene and xylene, alicyclic hydrocarbons such as cyclohexane,
Examples include aliphatic hydrocarbons such as n-hexane.

Examples of the radium salts used as catalysts in the present invention include palladium chloride, palladium bromide, palladium iodide, radium acetate, radium sulfate, and radium nitrate. Particularly preferred palladium salts as catalysts in the production method of the present invention are 7-radium chlorides, such as radium chloride and palladium bromide.

The catalyst (palladium salts) is generally 0.001 to 0.2 mol per mol of 3-phenylpropylene,
And preferably 0.005-0.08 mol is used.

If the amount of catalyst used is less than the lower limit of this range, the reaction will not proceed sufficiently, and even if the amount of catalyst used is more than the upper limit of the above range, it will hardly contribute to improving the reaction rate; This is not preferable because it becomes time consuming to recover the catalyst and also increases the loss of the catalyst during catalyst recovery.

The above reaction is carried out at a temperature of 0 to 150°C.

At temperatures higher than 150°C, side reactions such as isomerization reactions tend to proceed, and at temperatures lower than 0°C, the reaction rate decreases and is not practical. In addition, the particularly preferred reaction temperature for practical purposes is 10 to 90°C. The temperature is within the range of Also,
The reaction time varies depending on reaction conditions such as reaction temperature, but is generally selected from a range of 10 minutes to 5 hours.

There is no particular restriction on the pressure of the reaction system during the reaction, but usually,
A pressure in the range of normal pressure to 200 kg/cm'' (gauge pressure) is selected.

The present invention can be implemented, for example, by the following method.

A reaction vessel is charged with 3-phenylpropylene (raw material 1), alcohol, and a catalyst, and an alkyl nitrite ester is added thereto to allow the reaction to proceed under predetermined conditions. however,
There are no particular restrictions on the order in which these raw materials, catalysts, etc. are added.

After the reaction, No gas generated by distilling the reaction solution under reduced pressure,
Unreacted raw materials, alcohol, desired reaction products (1-phenyl-2,2-dialkoxypropanes), etc. are separated and obtained. The unreacted raw materials and alcohol recovered here can be recycled, and the No gas similarly recovered can also be used for the production of nitrite ester.

Next, examples of the present invention will be shown.

[Example 1] Raw material 3-(4-hydroxyphenyl)propylene 0.
10 moles, 0.25 moles of methyl nitrite, 0.5M of methyl alcohol, and 0.006 moles of noradium chloride as a catalyst.
Moles were charged into a reaction vessel, and the reaction was carried out under conditions of normal pressure, reaction temperature of 20° C., and reaction time of 1.5 hours.

After the reaction is completed, the reaction solution is subjected to gas chromatography to separate the unreacted raw materials in the reaction solution and the generated target product [1-(4-
hydroxyphenyl)-2,2-dimethoxypropane]
The reaction rate of the raw materials was 100% and the yield of the target product was 85%. Note that the reaction rate of the raw material and the yield of the target product are values calculated according to the following formula (the same applies to the following examples).

Reaction rate (%) of raw material [3-phenylpropylenes] = [
Reaction amount of raw material (mol) ÷ Amount of raw material charged (mol)] x 100 Yield of target product [l-phenyl-2,2-dialkoxypropanes] (%) = [Amount of target product produced (mol) ÷Amount of raw material charged (moles)]X100 [Example 2] Methyl nitrite and methyl alcohol were converted to nitrite
The same reaction as in Example 1 was carried out except that n-butyl and n-butyl alcohol were used and the reaction temperature was changed to 60°C. After the reaction is completed, the unreacted raw materials in the reaction solution and the generated target product [1-(4-hydroxyphenyl)] are separated in the same manner.
-2,2-di(n-butoxy)propane] was determined, and the reaction rate of the raw material was 100%, and the yield of the target product was 82%.

[Example 3] 3-(4-hydroxyphenyl)propylene was converted into 3-(4-hydroxyphenyl)propylene.
-Methoxyphenyl)propylene was used, but the same reaction as in Example 1 was carried out. After the reaction is completed, in the same way,
The unreacted raw materials in the reaction solution and the generated target product [1-(4-methoxyphenyl)-2,2-dimethoxypropane] were quantified, and the reaction rate of the raw materials was lOO%, and the yield of the target product was 94.
%. ' [Example 4] 3-(4-hydroxyphenyl)propylene was converted into 3-(4-hydroxyphenyl)
-Methoxyphenyl)propylene was used, but the same reaction as in Example 2 was carried out. After the reaction is completed, in the same way,
The unreacted raw materials and the formed target product [1-(4-methoxyphenyl)-2,2-di(n-butoxy)propane] in the reaction solution were determined, and the reaction rate of raw material 4 was 100%, and the target product was determined to be 100%. A yield of 89% was obtained.

[Example 5] 3-(4-hydroxyphenyl)propylene
-Hydroxy-3-methoxyphenyl)propylene was used, but the same reaction as in Example 1 was carried out. -Hydroxy-3-methoxyphenyl)-
2,2-dimethoxypropane] was quantitatively determined, and the reaction rate of the raw material was 100%, and the yield of the target product was 85%.

[Example 6] 3-(4-hydroxyphenyl)furopyrene was
-hydroxy-3-methoxyphenyl)propylene, and methyl nitrite and methyl alcohol are replaced with n-propyl nitrite and n-propyl alcohol, respectively;
Furthermore, the same reaction as in Example 1 was carried out except that the reaction temperature was changed to 30°C. After the reaction is completed, the unreacted raw materials and the generated target product [1-(4-hydroxy-3-methoxyphenyl)-2,2-di(n-propoxy)propane] in the reaction solution are determined in the same manner. , reaction rate of raw materials 100
%, and the yield of the target product was 83%.

[Example 7] 3-(4-hydroxyphenyl)propylene
The same reaction as in Example 2 was carried out except that -hydroxy-3-methoxyphenyl)propylene was used. After completion of the reaction, in the same manner, unreacted raw materials in the reaction solution and the generated target product [1-(4-hydroxy-3methoxyphenyl)-2
, 2-di(n-butoxy)propane].
The results showed that the reaction rate of the raw materials was 100% and the yield of the target product was 80%.

[Example 8] 3-(4-hydroxyphenyl)propylene was converted into 3-(
The same reaction as in Example 1 was carried out except that 3,4-dimethoxyphenyl)propylene was used. After the reaction is completed, the unreacted raw materials in the reaction solution and the generated target product [1-
(3,4-dimethoxyphenyl)-2,2-dimethoxypropane] was determined, and the i-size reaction rate was 100% and the yield of the target product was 93%.

[Example 9] 3-(4-hydroxyphenyl)propylene was converted into 3-(3
, 4-methylenedioxyphenyl)propylene was used, but the same reaction as in Example 1 was carried out. After the reaction is complete,
Similarly, the unreacted raw material 4 in the reaction solution and the generated target product [1-(3,4-methylenedioxyphenyl)-2,2
-dimethoxypropane] and the reaction rate of the raw materials was 100%, and the yield of the target product was 92%.

[Example 10] 3-(4-hydroxyphenyl)propylene
,4-dimethoxyphenyl)propylene, methyl nitrite and methyl alcohol were replaced with ethyl nitrite and ethyl alcohol, respectively, and the reaction temperature was changed to 30°C, but the same reaction as in Example 1 was carried out. After the completion of the 0 reaction, the unreacted raw materials in the reaction solution and the generated target product [1-(3,4-dimethoxyphenyl)-2,2-
jetoxypropane] and the reaction rate of the raw material 1
00%, and the yield of the target product was 90%.

[Example 11] 3-(4-hydroxyphenyl)propylene was converted into 3-(3
, 4-dimethoxyphenyl)propylene was used, but the same reaction as in Example 2 was carried out. After the reaction is completed, the unreacted raw materials in the reaction solution and the generated target product [1-(
3,4-dimethoxyphenyl)-2,2-di(n-butoxy)propane] and the reaction rate of the raw material was 100.
%, and the yield of the target product was 87%.

[Example 12] 3-(4-hydroxyphenyl)propylene
-Hydroxy-5-methoxy-3-nitrophenyl)propylene was used, except that the same reaction as in Example 1 was carried out. [1-(4-hydroxy-5-methoxy-3-nitrophe=71z)-2,2-'; methoxypropane] was quantitatively determined, and the reaction rate of the raw material was loo% and the yield of the target product was 83%. Got the results.

[Example 13] 3-(4-hydroxyphenyl)propylene
-Hydroxy-5-methoxy-3-trophenyl)propylene was used, but the same reaction as in Example 2 was carried out. [1-(4-hydroxy-5-methoxy-3-nitronenyl)-2,2-di(n-butoxy)
Propane] was determined, and the reaction rate of the raw materials was 100%, and the yield of the target product was 78%.

[Example 14] 3-(4-hydroxyphenyl)propylene
, 5-dimethoxy-3-nitrophenyl)propylene was used, but the same reaction as in Example 1 was carried out. After the reaction, the unreacted raw materials in the reaction solution and the generated target product [1-(4,5-dimethoxy-3-nitrophenyl)-2,2-dimethoxypropane J] were determined in the same manner, and the raw material A reaction rate of 100% and a yield of the target product of 86% were obtained.

[Example 15] 3-(4-hydroxyphenyl)propylene
, 5-dimethoxy-3-nitrophenyl) propylene was used. After the reaction was completed, the unreacted raw materials in the reaction solution and the generated target product [1 -(4,5-Simethoxy3-nitrophenyl)-2,2-di(n-butoxy)propane], and the reaction rate of the raw material was 100% and the yield of the target product was 82%. .

[Example 16] 3-(4-hydroxyphenyl)propylene
The same reaction as in Example 2 was carried out except that C17-4-methoxyphenyl)propylene was used instead. After the reaction is completed, the unreacted raw materials in the reaction solution and the generated target product [1-(3-chloro-4-methoxyphenyl)-2,
2-di(n-butoxy)propane] was determined, and the reaction rate of the raw materials was 100%, and the yield of the target product was 89%.

[Example 17] 3-(4-hydroxyphenyl)propylene was converted into 3-(3
-chloro-4-methoxyphenyl)propylene,
The same reaction as in Example 1 was carried out except that methyl nitrite and methyl alcohol were replaced with n-hexyl nitrite and n-hexyl alcohol, respectively, and the reaction temperature was changed to 60°C.

After completion of the reaction, in the same manner, unreacted raw material 4 in the reaction solution and the generated target product [1-(3-chloro-4-ethoxyphenyl)-2,2-(d-n-hexyloxy)propane] were separated. After quantitative determination, the reaction rate of the raw materials was 100%, and the yield of the target product was 8.
The result was 5%.

[Example 18] 3-(4-hydroxyphenyl)propylene was converted into 3-(
The same reaction as in Example 1 was carried out except that 3-bromo-4-ethoxyphenyl)propylene was used. After completion of the reaction, in the same manner, unreacted raw materials in the reaction solution and the generated target product (1-(3-bromo-4-ethoxyphenyl)-2,2
-dimethoxypropane] and the reaction rate of raw materials was 100%, and the yield of the target product was 90%.

[Example 19] 3-(4-hydroxyphenyl)propylene was converted into 3-(
Example 1 except that 3-7'romo-4-ethoxyphenyl)propylene was used, methyl nitrite and methyl alcohol were replaced with benzyl nitrite and benzyl alcohol, respectively, and the reaction temperature was changed to 60°C. After the completion of 6 similar reactions, in the same way, the unreacted raw materials in the reaction solution and the generated target product (1-(3-bromo-4-ethoxyphenyl)-2,2-dibenzyloxy)propane ]
- Left) was quantitatively determined, and the reaction rate of the raw materials was 100%, and the yield of the target product was 84%.

[Example 20] 3-(4-hydroxyphenyl)propylene
The same reaction as in Example 2 was carried out except that -methoxy-3-methylphenyl)propylene was used. After the reaction is complete,
Similarly, the unreacted raw materials in the reaction solution and the generated target product [
1-(4-methoxy-3-methylphenyl)-2,2-
Di(n-butoxy)propane] was quantitatively determined, and the reaction rate of the raw materials was 100%, and the yield of the target product was 88%.

[Example 21] 3-(4-hydroxyphenyl)propylene
-methoxy-3-methylphenyl)propylene,
The same reaction as in Example 1 was performed except that methyl nitrite and methyl alcohol were replaced with n-pentyl nitrite and n-pentyl alcohol, respectively, and the reaction temperature was changed to 60°C.

After the reaction is completed, the unreacted raw materials and the generated target product [1-(4-methoxy-3-methylphenyl)-2,2-(di-n-pentyloxy)propane] in one reaction solution are determined in the same manner. The reaction rate of raw materials was 100%, and the yield of the target product was 8.
The result was 6%.

[Example 22] The same reaction as in Example 1 was carried out except that 3-(4-hydroxyphenyl)furopylene was changed to 3-phenylpropylene. After the reaction is completed, the unreacted raw materials and the generated target product [l-phenyl-2,2-dimethoxypropane] in one reaction solution are determined in the same manner, and the reaction rate of the raw materials is 100%.
, the yield of the target product was 88%.

[Example 23] The same reaction as in Example 2 was carried out except that 3-(4-hydroxyphenyl)furopylene was changed to 3-phenylpropylene. 6 After the reaction, unreacted raw materials in the reaction solution were removed in the same manner. and the target product [l-phenyl-2,2-di(n
-butoxy)propane], and the reaction rate of the raw materials was 100%, and the yield of the target product was 85%.

[Example 24] 3-(4-hydroxyphenyl)propylene
The same reaction as in Example 1 was carried out except that the reaction mixture was changed to -amino-4-methoxyphenyl)propylene. After the reaction is complete,
Similarly, the unreacted raw materials in the reaction solution and the generated target product [
1-(3'-amino-4-methoxyphenyl)-2,2
-dimethoxypropane] and the reaction rate of the raw materials was 100%, and the yield of the target product was 86%.

[Example 25 Co-3-(4-hydroxyphenyl)propylene
The same reaction as in Example 2 was carried out except that -amino-4-methoxyphenyl)propylene was used. After the reaction is complete,
Similarly, unreacted raw materials in one reaction solution and the target product produced [
1-(3-amino-4-methoxyphenyl)-2,2-
Di(n-butoxy)propane] was determined, and the reaction rate of the raw materials was 100%, and the yield of the target product was 81%.

[Examples 26 to 29] Raw material 3-(4-hydroxy-3-methoxyphenyl)
Propylene 0.10 mol, nitrous tuna n -;/chill 0.2
5 moles, n-butyl alcohol 0.5 moles, and catalyst 0
．． 0.006 mole was charged into a reaction vessel, and the reaction temperature was 6 under normal pressure.
The reaction was carried out at 0° C. for 1.5 hours.

After completion of the reaction, in the same manner as in Example 1, the unreacted raw materials in the reaction solution and the generated target product (1-(4-hydroxy-3-methoxyphenyl)-2,2-di(n-butoxy)propane) was quantified.

Table 1 shows the catalysts used and the results obtained.

Table 1 Example Catalyst Reaction rate of raw material to target product Yield 26 Palladium bromide 100% 84%27
Palladium acetate 53% 19%28 Palladium nitrate 73% 29%29 Palladium sulfate 50% 18% [Examples 30 to 33] 0.10 mol of 3-(3,4-dimethoxyphenyl)propylene in 14, n-butyl nitrite 0.25-F-le, n
-Butyl alcohol (0.51°) and catalyst (0.006 mol) were placed in a reaction vessel, and the reaction was carried out under normal pressure, reaction temperature: 60° C., and reaction time: 1.5 hours. After completion of the reaction, in the same manner as in Example 1, the unreacted raw materials in the reaction solution and the generated target product [1-(3,4-dimethoxyphenyl)-2
, 2-di(n-butoxy)propane] was determined.

Table 2 shows the catalysts used and the results obtained.

Table 2 Examples Catalyst Reaction rate of raw material to target product Yield 30 Palladium bromide 100% 90%31
Palladium acetate 60% 23%32 Palladium nitrate 77% 36%33 Palladium sulfate 56% 23% [Examples 34-35] Raw materials 3-(3-chloro-4-methoxyphenyl)propylene 0.10 mol, nitrous acid n - 0.25 mole of butyl, 0.5 mole of n-butyl alcohol, and 0.00 mole of catalyst
6 mol was charged into a reaction vessel, and the reaction temperature was 60°C under normal pressure.
The reaction was carried out under conditions of a reaction time of 1.5 hours. After completion of the reaction, in the same manner as in Example 1, the unreacted raw materials in the reaction solution and the generated target product [1-(3-chloro-4-methoxyphenyl)-2,2-di(n-butoxy)propane] was quantified.

Table 3 shows the catalysts used and the results obtained.

Table 3 Examples Catalyst Reaction rate of raw material to target product Yield 34 Palladium bromide ioo% 92% 35
Palladium acetate 62% 28% [Example 36
~37] Raw materials 3-(4-nithoxy-2-methylphenyl)propylene 0.10 mol, n-butyl nitrite 0.25 mol,
0.5 sentences of n-butyl alcohol.

Then, 0.006 mol of catalyst was charged into a reaction vessel, and the reaction was carried out under conditions of normal pressure, reaction temperature of 60° C., and reaction time of 1.5 hours. After the reaction is completed, in the same manner as in Example 1, the unreacted raw materials in the reaction solution and the generated target product [1-(4-
ethoxy-2-methylphenyl)-2,2-di(n-butoxy)propane] was determined.

Table 4 shows the catalysts used and the results obtained.

Table 4 Example Catalyst Reaction rate of raw material to target product Yield 36 Palladium bromide 100% 87% 37
Palladium nitrate 66% 31% [Example 38
~39] Raw materials 3-(4,5-dimethoxy-3-nitrophenyl)propylene 0.10 mol, nitrous n-butyl 0.2
5 moles, 0.5 moles of n-butyl alcohol, and 0 catalyst
．． 0.006 mole was charged into a reaction vessel, and the reaction temperature was 6 under normal pressure.
The reaction was carried out at 0° C. for a reaction time of 1.5 hours.

After completion of the reaction, in the same manner as in Example 1, the unreacted raw materials in the reaction solution and the generated target product [1-(4,5-dimethoxy-3
-nitrophenyl)-2,2-di(n-butoxy)propane] was determined.

Table 5 shows the catalysts used and the results obtained.

Table 5 Example Catalyst Reaction rate of raw material to target product Yield 38 Palladium nitrate 70% 39%39
Palladium sulfate 58% 27% I [Examples 40-41] Raw materials 3-phenylpropylene 0.10 mol, nitrous acid n
- 0.25 mol of butyl, 0.5 mole of n-butyl alcohol, and 0.006 mol of catalyst were charged into a reaction vessel, and the reaction was carried out under normal pressure, 60°C per reaction part, and reaction time of 1.5 hours. Ta. After completion of the reaction, in the same manner as in Example 1, unreacted raw materials in one reaction solution and the generated target product [l-phenyl-
2,2-di(n-butoxy)propane] was determined.

Table 6 shows the catalysts used and the results obtained.

Table 6 Example Catalyst Reaction rate of raw material to target product Yield 40 Palladium bromide 100% 90%41
Palladium acetate 56% 22% [Example 42
~43] Raw materials 3-(3-amino-4-methoxyphenyl)propylene 0.10 mol, n-butyl nitrite 0.25 mol,
0.5 grams of n-butyl alcohol, and 0.006 grams of catalyst
Charge the mole into the reaction vessel.

The reaction was carried out under conditions of normal pressure, reaction temperature of 60° C., and reaction time of 1.5 hours. After the reaction is completed, in the same manner as in Example 1, the unreacted raw materials in the reaction solution and the generated target product [1-(3-
Amino-4-methoxyphenyl)-2,2-di(n-butoxy)propane] was determined.

Table 7 shows the catalysts used and the results obtained.

Table 7 Example Catalyst Reaction rate of raw material to target product Yield 42 Palladium bromide 100% 88% 43
Palladium nitrate 71% 35% Procedural amendment dated 1971, April 19, 1982, Japan Patent Office, Kazuo Wakasugi, 1, Indication of the case, 1982, Patent Application No. 108526, 2, Name of the invention: S /-phenyl-2,2-dialkoxy Propane manufacturing method 3, Relationship with the case of the person making the amendment Patent applicant 4, Attorney 6 Number of inventions increased by amendment None 7, Subject of amendment “Claims column”, Details of P invention "Explanation column"
8. Contents of the amendment [I] Amendment to the scope of claims - As per the attached sheet [I[
] Amendment to the Detailed Description of the Invention (1) Page 7, line 7, [methyl alcohol ethyl] is corrected to [methyl alcohol, ethyl].

(2) Page 11, line 1-2, page 23, line 1 from the bottom, page 25, 2
line, page 26, line 4, page 27, line 4, page 28, line 4, 2
On page 9, line 3, on page 30, line 3 and above, it says,
” to be deleted.

(3) Page 4, line 9, “and lower alkoxy groups with 6 or less carbon atoms, etc.”
Lower alkoxy groups, benzyloxy groups, etc. of up to 6 prime numbers.''

(4) In the first line from the bottom of page 4, "a group consisting of a ru group and a lower alkoxy group" is corrected to "a group consisting of a ru group, a lower alkoxy group, and a benzyloxy group".

(5) After [Example 25] on page 23 (between lines 14 and 15), the following [Example 26] and [Example 27]
to join.

[Example 26] 3-(4-hydroxyphenyl)propylene
The same reaction as in Example 1 was carried out except that -benzyloxy-3-methoxyphenyl)propylene was used. After the reaction is completed, the unreacted raw materials in the reaction solution and the generated target product [1-(4-benzyloxy-3-methoxyphenyl)-2゜2-dimethoxypropane] are determined in the same manner, and the reaction of the raw materials is determined. The yield of the target product was 90%.

[Example 27] 3-(4-hydroxyphenyl)propylene
The same reaction as in Example 1 was carried out except that the reaction mixture was changed to -methoxy-3-benzyloxyphenyl)propylene. After the reaction is completed, the unreacted raw materials in one reaction solution and the generated target product [1-(4-methoxy-3-benzyloxyphenyl)-2゜2-dimethoxypropane] are determined in the same manner, and the reaction of the raw materials is determined. The yield of the target product was 90%. 1 (6)
The numbers of each example on page 23, line 15 and below are changed as follows.

a) Page 23, line 15 [Examples 26-29] → [Examples 28-31] b) 24
Example numbers 26.2728 and 29 in Table 1 on page 1 are corrected to 28.29.3° and 31, respectively.

c) 4 lines from the bottom of page 24 [Examples 30-33] → C Examples 32-35] d) 25
Example numbers 3o, 3132 and 33 in Table 2 on page 2 are corrected to 32.33.34 and 35, respectively.

e) 2 lines from the bottom of page 25 [Examples 34-35] → rExamples 36-37] f) 26
Example numbers 34 and 35 in Table 3 on page 3 are corrected to 36 and 37, respectively.

g) 2 lines from the bottom of page 26 [Examples 36-37] → [Examples 38-39] h) 27
Example numbers 36 and 37 in Table 4 on page 4 are corrected to 38 and 39, respectively.

1) 2 lines from the bottom of page 27 [Examples 38-39] → [Examples 40-41] j) 28
Example numbers 38 and 39 in Table 5 on page 5 are corrected to 40 and 41, respectively.

k) 2 lines from the bottom of page 28 [Examples 40-41] → [Examples 42-43] 1) 29
Example numbers 40 and 41 in Table 6 on page 6 are corrected to 42 and 43, respectively.

m) 2 lines from the bottom of page 29 [Examples 42-43] → [Examples 44-45] n) 30
Example numbers 42 and 43 in Table 7 on page 7 are corrected to 44 and 45, respectively.

Claims (after correction) 1゜Reacting 3-phenylpropylene, which may have a substituent on the benzene ring, with an alkyl nitrite ester in the presence of a catalyst of alcohol and nogradium salt. A method for producing 1-phenyl-2,2-dialkoxypropanes, characterized by:

2. The method for producing 1-phenyl-2,2-dialkoxypropanes according to claim 1, characterized in that no substituent is present on the benzene ring of 3-phenylpropylene.

3. Hydroxyl group on the benzene ring of 3-phenylpropylene,
Halogen atom, nitro group, amine group, lower alkyl group,
1-phenyl-2,2-dialkoxy according to claim 1, characterized in that 1 to 3 substituents selected from the group consisting of a lower alkoxy group and benzid are present. Propanes - Method of production.
,,14. In the benzene ring of 3-phenylpropylene, there is a substituent that forms a 5- to 7-membered heterocycle containing 1 to 2 oxygen atoms together with a part of the benzene ring. Characteristic claim 1
A method for producing 1-phenyl-2,2-dialkoxypropanes as described in 1.

5. The alkyl part of the nitrite alkyl ester has 1 carbon atoms.
1-phenyl-2 according to claim 1, which is an alkyl group or benzyl group of ~1O
, 2-dialkoxypropane production method.

1-phenyl-2,2- according to claim 5, characterized in that the alkyl moiety constituting the 6° alcohol is the same as the alkyl moiety of the nitrite alkyl ester.
A method for producing dialkoxypropanes.

The method for producing 1-phenyl-2,2-dialkoxypropanes according to claim 1, wherein the palladium salt of the 7° catalyst is a palladium halide.

Procedural amendment document March 22, 1980 Patent Office Kazuo Wakasugi 1, Indication of the case 1988 Patent Application No. 108526 3, Person making the amendment Relationship with the case Patent applicant 4, Agent 6, By amendment Increasing number of inventions None The column for detailed description of inventions will be amended as follows.

(1) Add the following [Example 26] and [Example 27] after [Example 25] on page 23 (after the 14th line).

[Example 26] 3-(4-hydroxyphenyl)propylene is 3-(
The same reaction as in Example 1 was carried out except that 2-hydroxyphenyl)propylene was used. After the reaction was completed, the unreacted raw materials in the reaction solution and the generated target product [1-
-Hydroxyphenyl)-2,2-dimethoxypropane] and the reaction rate of the raw material was 100%, and the yield of the target product was 86%.

[Example 27] 3-(4-hydroxyphenyl)propylene was converted into 3-(2-hydroxyphenyl)propylene.
-Methoxyphenyl)propylene was used, but the same reaction as in Example 1 was carried out. After the reaction is completed, in the same way,
The unreacted raw materials in the reaction solution and the generated target product (1-(2-methoxyphenyl)-2,2-dimethoxypropane) were quantified, and the reaction rate of the raw materials was 100%, and the yield of the target product was 92%.
%.

(2) Specification submitted at the time of filing the application and 1981 l
The number of each example after [Example 26] written in the written amendment submitted on October 19th is the above [Example 26]
and the additional side of [Example 27].

For reference, each new example (with a new number) after [Example 26] is described in a separate sheet.

Attachment: Procedural amendment dated October 19, 1981 [Example 26] 3-(4-hydroxyphenyl)propylene is
The same reaction as in Example 1 was carried out except that 2-hydroxyphenyl)propylene was used. After the reaction is completed, the unreacted raw materials in the reaction solution and the generated target product [1-(2
-Hydroxyphenylene Jl/)-2,2-dimethoxypropane]: 100% reaction rate of raw materials
, the yield of the target product was 86%.

[Example 27] 3-(4-hydroxyphenyl)propylene was converted into 3-(2-hydroxyphenyl)propylene.
-Methoxyphenyl)propylene was used, but the same reaction as in Example 1 was carried out. After the reaction is completed, in the same way,
The unreacted raw materials in the reaction solution and the generated target product (1-(2-methoxyphenyl)-2,2-dimethoxypropane) were quantified, and the reaction rate of the raw materials was 100%, and the yield of the target product was 92%.
%.

[Example 28] 3-(4-hydroxyphenyl)propylene
The same reaction as in Example 1 was carried out except that -benzyloxy-3-methoxyphenyl)propylene was used. After completion of the reaction, in the same manner, the amount of unreacted raw material and the generated target product (1-(4-benzyloxy-3-methoxyphenyl)-2゜2-dimethoxypropane) in the reaction solution was determined by an order of magnitude. A reaction rate of 100% and a yield of the target product of 90% were obtained.

[Example 29] 3-(4-hydroxyphenyl)furopyrene
The same reaction as in Example 1 was carried out except that the reaction mixture was changed to -methoxy-3-benzyloxyphenyl)propylene. After the reaction, the unreacted raw materials in the reaction solution and the generated target product [1-(4-methoxy-3-benzyloxyphenyl)-2゜2-dimethoxypropane] are determined in the same manner, and the reaction of the raw materials is determined. The yield of the target product was 90%.

[Examples 30 to 33] Raw material 3-(4-hydroxy-3-methoxyphenyl)
Propylene 0.10 mol, n-methyl nitrite 0.25
mole, 0.5 mole of n-butyl alcohol, and 0.5 mole of catalyst.
006 mol was charged into a reaction vessel, and the reaction was carried out at a reaction temperature of 60° C. and a reaction time of 1.5 hours. After completion of the reaction, in the same manner as in Example 1, the unreacted raw materials in the reaction solution and the generated target product [1-(4-hydroxy-3-methoxyphenyl)-2,2-di(n-butoxy)propane] was quantified.

Table 1 shows the catalysts used and the results obtained.

Table 1 Example Catalyst Reaction rate of raw material to target product Yield 30 Palladium bromide 100% 84%31
Palladium acetate 53% 19%31 Palladium nitrate 73% 29%33 Palladium sulfate 50% 18% [Examples 34 to 37] [14 3-(3,4-dimethoxyphenyl)propylene 0.10 mol, nitrous acid n- Butyl 0°25 mol, n-
0.5 mole of butyl alcohol and 0.006 mole of catalyst were charged into a reaction vessel, reaction temperature: 60°C, reaction time: 1.
The reaction was carried out for 5 hours. After the reaction was completed, the same procedure as in Example 1 was carried out and the unreacted raw materials in the reaction solution and the produced target product [1-(3
, 4-dimethoxyphenyl)-2,2-di(n-butoxy)propane].

Table 2 shows the catalysts used and the results obtained.

Table 2 Example Catalyst Reaction rate of raw material to target product Yield 34 Palladium bromide 100% 90% 35
Palladium acetate 60% 23%36 Palladium nitrate 77% 36%37 Palladium sulfate 56% 23% [Examples 38-39] Raw materials 3-(3-chloro-4-methoxyphenyl)propylene 0.10 mol, nitrous acid n -butyl 0.25 mol,
n-butyl alcohol 0.5 grams, and catalyst 0.00~
Charge 6 mol into the reaction vessel.

The reaction was carried out at a reaction temperature of 60° C. and a reaction time of 1.5 hours. After completion of the reaction, in the same manner as in Example 1, unreacted raw materials in one reaction solution and the generated target product (1-(3-chloro-
4-methoxyphenyl)-2,2-di(n-butoxy)
Propane] was determined.

Table 3 shows the catalysts used and the results obtained.

Table 3 Example Catalyst Reaction rate of raw material to target product Yield 38 Palladium bromide 100% 92% 39
Palladium acetate 62% 28% [Example 40
~411 Raw materials 3-(4-ethoxy-2-methylphenyl)propylene 0.10 mol, n-butyl nitrite 0.25 mol,
0.5 grams of n-butyl alcohol, and 0.006 grams of catalyst
A mol was charged into a reaction vessel, and the reaction was carried out at a reaction temperature of 60° C. and a reaction time of 1.5 hours. After completion of the reaction, in the same manner as in Example 1, the unreacted raw material' in the reaction solution and the generated target product [1-(4-ethoxy-2-methylphenyl)]
-2.2-di(n-butoxy)propane] was determined.

Table 4 shows the catalysts used and the results obtained.

Table 4 Example Catalyst Reaction rate of raw material to target product Yield 40 Palladium bromide 100% 87% 41
Palladium nitrate 66% 31% [Example 42
~43] Raw materials 3-(4,5-dimethoxy-3-nitrophenyl)propylene 0.10 mol, n-butyl nitrite 0.25
mol, n-butyl alcohol 0.5 mole, and catalyst o
, oos moles were charged into a reaction vessel, and the reaction temperature was 60°C1.
The reaction was carried out under the conditions of a reaction time of 1.5 hours. After the completion of the reaction, the unreacted raw materials in the reaction solution and the generated target product [1-(4,5-dimethoxy-3 -nitrophenyl)-2,2-di(n-butoxy)propane]
was quantified.

Table 5 shows the catalysts used and the results obtained.

Table 5 Example Catalyst Reaction rate of raw material to target product Yield 42 Palladium nitrate 70% 39%43
Palladium sulfate 58% 27% [Example 44
~45] Raw materials 3-phenylpropylene 0.10 mol, nitrous acid n
-Butyl 0.25 mol, n-butyl alcohol 0.5 M
Then, 0.006 mol of the catalyst was charged into a reaction vessel, and the reaction was carried out under the following conditions: 1 reaction temperature was 60° C., and the reaction time was 1° and 5 hours. After completion of the reaction, in the same manner as in Example 1, the unreacted raw materials in the reaction solution and the generated target product [l-phenyl-2,2-
di(n-butoxy)propane] was determined.

Table 6 shows the catalysts used and the results obtained.

Table 6 Example Catalyst Raw material Target 1
Reaction rate Yield 4
4 Palladium bromide 100% 90%45 Palladium acetate 56% 22% [Example 46~
47] Raw materials: 0.10 mol of 3-(3-amino-4-methoxyphenyl)propylene, 0.25 mol of n-butyl nitrite, 0.5 Jl of n-butyl alcohol.

Then, 0.006 mol of the catalyst was charged into a reaction vessel, and the reaction was carried out under the conditions of a reaction temperature of 60°C and a reaction time of 1.5 hours. The raw materials and the produced target product [1-(3-amino-4-methoxyphenyl)-2,2-di(n-butoxy)propane] were quantitatively determined.

Table 7 shows the catalysts used and the results obtained.

Table 7 Example Catalyst Reaction rate of raw material to target product Yield 46 Palladium bromide 100% 88% 47
Palladium nitrate 71% 35% - or more

Claims (1)

[Claims] 1. 3-phenylpropylenes which may have a substituent on the benzene ring are reacted with an alkyl nitrite ester in the presence of a catalyst of alcohol and palladium salts. A method for producing l-phenyl-2,2-dialkoxypropanes. 2. The method for producing 1-phenyl-2,2-dialkoxypropanes according to claim 1, characterized in that no substituent is present on the benzene ring of 2゜3-phenylpropylene. 3. Hydroxyl group on the benzene ring of 3-phenylpropylene,
halogen atom, nitro group, amino group, lower alkyl group,
Production of 1-°phenyl-2,2-dialkoxypropanes according to claim 1, characterized in that 1 to 3 substituents selected from the group consisting of lower alkoxy groups are present. Method. 4. 5 containing 1 to 2 oxygen atoms in the benzene ring of 3-phenylpropylene in collaboration with a part of the benzene ring
1-phenyl-2 according to claim 1, characterized in that a substituent forming a ~7-membered heterocycle is present;
Method for producing 2-dialkoxypropanes. 5゜The alkyl part of the nitrite alkyl ester has 1 carbon number
1-phenyl-2 according to claim 1, which is an alkyl group or a benzyl group of ~10
, 2-dialkoxypropane production method. 6. 1-phenyl-2,2- according to claim 5, wherein the alkyl moiety constituting the alcohol is the same as the alkyl moiety of the nitrite alkyl ester.
A method for producing dialkoxypropanes. 7. The method for producing 1-phenyl-2,2-dialkoxy, propanes according to claim 1, wherein the palladium salt of the catalyst is a /\logonide of palladium.