JP2910276B2 - Method for producing monoesters of diols - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a monoester of a diol represented by the following general formula (2).
The monoesters of the above-mentioned diols are useful compounds used as, for example, monomers of polymers having plasticity. (European Patent EP 316918-A
² )

[0002]

2. Description of the Related Art As a method for obtaining monoesters of diols, a method of coupling a carboxylic acid or a derivative thereof with a diol is well known. Therefore, it is hard to say that the production method is industrially advantageous. Also, a method of oxidizing a cyclic acetal (Can. J. Chem., 52 , 3651 (1974))
And J. Chem. Soc., Chem. Commun., 1245, (1983)), these methods cannot be said to be industrially advantageous production methods such as requiring a low temperature and having a long reaction time.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for producing monoesters of diols which solves the various problems described above.

[0004]

Means for Solving the Problems The present inventors have conducted various studies in order to solve the above-mentioned problems, and have reached the present invention. That is, the present invention provides a compound represented by the general formula 1

[0005] (Wherein, R is a linear, branched or cyclic alkyl group having 1 to 15 carbon atoms; or a phenyl group, a phenyl lower alkyl group or a phenyl lower alkenyl group, wherein
Phenyl may have a lower alkyl group, a halogen atom, or a lower alkoxy group as a substituent. Or a lower alkyl group having a cyano group, a lower alkylcarbonyl group or a lower alkoxycarbonyl group as a substituent, and n represents 2, 3 or 4. A) reacting a cyclic acetal represented by the formula (1) with t-butyl hydroperoxide in the presence of a ruthenium catalyst;

[0006] (Wherein, R and n have the same meanings as described above).

The cyclic acetal represented by the above general formula 1 used as a raw material in the present invention includes, for example, 2-methyl-1,3-dioxolan, 2-n-hexyl-1,3-dioxolan, n-heptyl-1,
3-dioxolan, 2-n-pentadecyl-1,3-dioxolan, 2-n-hexyl-1,3-dioxane,
2-n-hexyl-1,3-dioxepane, 2-isopropyl-1,3-dioxolan, 2-cyclohexyl-
1,3-dioxolan, 2-phenyl-1,3-dioxolan, 2- (4′-methoxyphenyl-1,3-dioxolan, 2- (3 ′, 4′-methylenedioxyphenyl) -1,3- Dioxolan, 2-p-tolyl-1,3
-Dioxolan, 2- (4'-ethylphenyl) -1,
3-dioxolan, 2- (4'-chlorophenyl)-
1,3-dioxolan, 2- (4'-bromophenyl)
-1,3-dioxolan, 2- (3′-chlorophenyl) 1,3-dioxolan, 2-phenyl-1,3-dioxane, 2-phenyl-1,3-dioxepane, 2-
Benzyl-1,3-dioxolan, 2- (4′-chlorobenzyl) -1,3-dioxolan, 2- (2′-oxopropyl) -1,3-dioxolan, 2- (2′-oxopropyl)- 1,3-dioxane, 2-methoxycarbonylmethyl-1,3-dioxolan, 2-ethoxycarbonylmethyl-1,3-dioxolan, 2-cyanomethyl-1,3-dioxolan, 2-cyanomethyl-
1,3-dioxane, 2- (1′-propenyl) -1,
3-dioxolan, 2- (2'-phenylvinyl)-
1,3-dioxolan, 2- (2′-phenylvinyl)
-1,3-dioxane and the like.

Examples of the ruthenium catalyst include ruthenium trichloride hydrate, dihydridoterakis (triphenylphosphine) ruthenium, dodecacarbonyltriruthenium, dichlorobis (2,2'-bipyridyl) ruthenium and dichlorotris (triphenylphosphine) ruthenium. And the amount of use is not particularly limited,
Usually, it is used in the range of 0.1 mol% to 20 mol%, preferably 1 mol% to 20 mol%, based on the cyclic acetal. The amount of t-butyl hydroperoxide used is in the range of 1 to 5 equivalents based on the cyclic acetal.

In the present invention, a reaction solvent is not particularly required, but when a solvent is used, an inert solvent such as benzene, monochlorobenzene, dichloromethane and the like can be used. Although the amount of the solvent used is not particularly limited, it is usually used in a range of 0.5 to 9 times by weight based on the cyclic acetal.

[0010] The reaction temperature is generally in the range of 0 ° C to the reflux temperature of the reaction mixture, preferably in the range of 20 ° C to 50 ° C. The reaction time is not particularly limited, but the reaction mixture may be analyzed by GC or the like, and the point at which the cyclic acetal as the raw material disappears may be regarded as the reaction end point. Usually 4 after the end of dripping
It will be the reaction end point in about 5 hours.

After the completion of the reaction, for example, an aqueous solution of sodium sulfite is added to the reaction mixture, and the mixture is stirred to decompose the remaining peroxide. Can be obtained.

[0012]

The present invention is a method for reacting readily available t-butyl hydroperoxide with a cyclic acetal under mild conditions using a low-toxicity and easily prepared ruthenium complex as a catalyst. The reaction time is as follows: This is a method for producing an excellent diol monoester which is short and does not produce a diester.

[0013]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the present invention is limited thereto.

Examples 1 to 5 and Comparative Example 1 2-phenyl-1,3-dioxolane 300 mg, 2-phenyl-1,3-dioxolane
To a mixture of 3 mol% of catalyst with respect to phenyl-1,3-dioxolane and 2.0 ml of benzene at 25 ° C.
0.56 ml of a 55 M t-butyl hydroperoxide benzene solution was added dropwise over 1 hour. After stirring the reaction mixture at the same temperature for another 1 hour, it was analyzed by GC, and the results shown in Table 1 were obtained. The product (monoester of benzoic acid and ethylene glycol) was quantified by GC-IS.

[Table 1] Example Catalyst conversion rate ^{* 1} (% ) Yield ^{* 2} (%) 1 Cat-1 93.3 76.8 2 Cat-2 75.7 64.2 3 Cat-3 78.0 59.6 4 Cat-4 59.7 55.7 5 Cat -5 75.3 51.5 Comparative Example 1 None 0.0 0.0 mm ─Note) Cat-1: Ruthenium trichloride hydrate Cat-2: Dihydridotetrakis (triphenylphosphine) ruthenium Cat-3: Dodecacarbonyltriruthenium Cat-4: Dichlorobis (2,2′-bipyridyl) ruthenium Cat-5 : dichloro tris (triphenylphosphine) ruthenium ^{* 1} to 2-phenyl-1, - dioxolane ^{* 2} to 2-phenyl-1,3-dioxolane

Example 6 2- (n-hexyl) -1,3-dioxolane 949 m
g, 47 mg of ruthenium trichloride hydrate and 6.0 ml of benzene, at 25 ° C., 5.07 ml of a 3.55 M t-butyl hydroperoxide benzene solution was added dropwise over 1 hour. After the reaction mixture was further stirred at the same temperature for 4 hours, a solution obtained by adding ether to the reaction mixture was passed through florisil column chromatography, and eluted with ether. The oily substance obtained by concentrating the ether solution under reduced pressure was purified by controlled thin-layer chromatography, and 751 mg of a monoester of heptanoic acid and ethylene glycol was obtained (yield 7).
1.9%) as a colorless oil. ¹ H-NMR (CDCl ₃ ) δ 4.21 (m, 2H), 3.82 (m, 2H),
2.44 (m, 1H), 2.35 (t, 2H, J = 7.
6 Hz), 1.63 (m, 2H), 1.30 (m, 6
H), 0.89 (t, 3H, J = 7.1 Hz) IR (neat) 3460, 1738, 1173 cm ^-1 MS (HRCI) m / z 175, 1334 (calculated as C ₉ H ₁₈ O ₃ 175 , 1334)

Example 7 The same operation as in Example 6 was carried out except that 901 mg of 2-phenyl-1,3-dioxolan was used instead of 2- (n-hexyl) -1,3-dioxolan, and benzoic acid and ethylene were used. 787 mg of a monoester with glycol (78.9% yield) was obtained as a colorless oil. ¹ H-NMR (CDCl ₃ ) δ 8.05 (m, 2H), 7.38 to 7.58 (m,
3H), 4.44 (m, 2H), 3.93 (m, 2
H), 2.59 (brs, 1H)) IR (neat) 3444, 1721, 1279 cm ^-1 MS (HRCI) m / z 167, 0714 (calculated as C ₉ H ₁₀ O ₃ 167, 0708)

Example 8 The same operation as in Example 6 except that 1.08 g of 2- (4'-methoxyphenyl) 1,3-dioxolane was used instead of 2- (n-hexyl) -1,3-dioxolane. Was carried out to obtain 944 mg (yield: 80.2%) of a monoester of p-methoxybenzoic acid and ethylene glycol as a pale yellow oily substance. ¹ H-NMR (CDCl ₃ ) δ 8.00 (m, 2H), 6.90 (m, 2H),
4.42 (m, 2H), 3.93 (m, 2H), 3.8
5 (s, 3H), 2.48 (brs, 1H)) IR (n
^{eat) 3450,1713,1279cm -1 MS (HRCI)} m / z 197,0803 ( calcd 197,0814 as C ₁₀ H ₁₃ O ₄₎

Example 9 2- (p-tolyl) -1,3-dioxolan 985 m instead of 2- (n-hexyl) -1,3-dioxolan
The same operation as in Example 6 was performed except that g was used, and p-
927 mg (85.7% yield) of a monoester of methylbenzoic acid and ethylene glycol was obtained as a colorless oil. ¹ H-NMR (CDCl ₃ ) δ 7.94 (d, 2H, J = 8.3 Hz), 7.22
(D, 2H, J = 8.3 Hz), 4.43 (ddd, 2
H, J = 5.9 Hz, 3.2 Hz, 1.2 Hz), 3.
93 (ddd, 2H, J = 5.9 Hz, 3.2 Hz,
1.2Hz), 2.46 (brs, 1H), 2.40
(S, 3H) IR (neat ) 3439,1715,1281cm -1 MS (HREI) m / z 180,0798 ( calcd 180,0786 as C ₁₀ H ₁₂ O ₃₎

Example 10 The same operation as in Example 6 except that 1.11 g of 2- (4'-chlorophenyl) -1,3-dioxolan was used instead of 2- (n-hexyl) -1,3-dioxolan. Was performed to obtain 1.05 g (yield: 87.1%) of a monoester of p-chlorobenzoic acid and ethylene glycol as a pale yellow oil. ¹ H-NMR (CDCl ₃ ) δ 7.97 (m, 2H), 7.40 (m, 2H),
4.45 (m, 2H), 3.94 (m, 2H), 2.5
9 (brs, 1H)) IR (neat) 3432, 1721, 1275 cm ^-1 MS (HRCI) m / z 201, 0308 (calculated as C ₉ H ₁₀ O ₃ Cl 201, 0318)

Example 11 The same operation as in Example 6 was carried out except that 1.11 g of 2- (3'-chlorophenyl-1,3-dioxolane was used instead of 2- (n-hexyl) -1,3-dioxolane. This gave 971 mg (yield 80.6%) of a monoester of m-chlorobenzoic acid and ethylene glycol as a pale yellow oil ¹ H-NMR (CDCl ₃ ) δ 8.02 (dd, 1H, J) = 2.2Hz, 1.5H
z), 7.93 (ddd, 1H, J = 7.8 Hz, 1.D).
5Hz, 1.2Hz), 7.53 (ddd, 1H, J =
7.8Hz, 2.2Hz, 1.2Hz), 7.37
(T, 1H, J = 7.8 Hz), 4.46 (m, 2
H), 3.96 (m, 2H), 2.37 (brs, 1
H) IR (neat) 3430, 1725, 1292, 1260 cm ^-1 MS (HREI) m / z 200, 0218 (calculated as C ₉ H ₉ O ₃ Cl 200, 0240)

Example 12 The same operation as in Example 6 was carried out except that 985 mg of 2-phenyl-1,3-dioxane was used instead of 2- (n-hexyl) -1,3-dioxolane, and benzoic acid and 1 624mg of monoester with 3,3-propanediol
(57.7% yield) as a colorless oil. ¹ H-NMR (CDCl ₃ ) δ 8.03 (m, 2H), 7.54 (m, 1H),
7.43 (m, 1H), 4.49 (t, 2H, J = 6.
1 Hz), 3.78 (t, 2H, J = 6.1 Hz),
2.25 (brs, 1H), 2.01 (tt, 2H, J
= 6.1 Hz) IR (neat) 3420, 1721, 1277 cm ^-1 MS (HRCI) m / z 181, 0865 (calculated as C ₁₀ H ₁₃ O ₃ 181, 0865)

Example 13 The same operation as in Example 6 was carried out except that 1.07 g of 2-phenyl-1,3-dioxepane was used instead of 2- (n-hexyl) -1,3-dioxolane, and benzoic acid was used. And monoester of 1,4-butanediol 539mg
(46.3% yield) as a pale yellow oil. ¹ H-NMR (CDCl ₃ ) δ 8.03 (m, 2H), 7.55 (m, 1H),
7.42 (m, 2H), 4.36 (t, 2H, J = 6.
3 Hz), 3.71 (t, 2H, J = 6.6 Hz),
1.67~1.92 (m, 5H) IR ( neat) 3416,1719,1277cm -1 MS (HREI) m / z 194,0950 ( calcd 194,0943 as C ₁₁ H ₁₄ O ₃₎

Example 14 The same operation as in Example 6 was carried out except that 985 mg of 2-benzyl-1,3-dioxolan was used instead of 2- (n-hexyl) -1,3-dioxolan, and phenylacetic acid and ethylene were used. 666mg of monoester with glycol
(61.6% yield) as a pale yellow oil. ¹ H-NMR (CDCl ₃ ) δ 7.22 to 7.35 (m, 5H), 4.21 (m,
2H), 3.77 (m, 2H), 3.66 (s, 2
H), 2.22 (brs, 1H ) IR (neat) 3460,1736,1161cm -1 MS (HRCI) m / z 181,0870 ( calcd 181,0865 as C ₁₀ H ₁₃ O ₃₎

Example 15 The same operation as in Example 6 was carried out except that 781 mg of 2- (2'-oxopropyl) -1,3-dioxolan was used instead of 2- (n-hexyl) -1,3-dioxolan. This gives a monoester of acetoacetic acid and ethylene glycol.

Example 16 The same operation as in Example 6 was carried out except that 961 mg of 2-ethoxycarbonylmethyl-1,3-dioxolane was used instead of 2- (n-hexyl) -1,3-dioxolane, and malonic acid was used. 333 mg (yield 31.5%) of a mixed ester of ethanol and ethylene glycol was obtained. ¹ H-NMR (CDCl ₃ ) δ 4.30 (m, 2H), 4.22 (q, 2H, J =
7.3 Hz), 3.83 (m, 2H), 3.42 (s,
2H), 2.57 (brs, 1H), 1.29 (t, 3
H, J = 7.3 Hz)) IR (neat) 3507, 1734 cm ^-1 MS (HRCI) m / z 177, 0757 (calculated as C ₇ H ₁₃ O ₅ 177, 0763)

Example 17 2-cyanomethyl-1,3-dioxolan 679 mg instead of 2- (n-hexyl) -1,3-dioxolan
Is carried out in the same manner as in Example 6 except that the monoester of malononitrile and ethylene glycol is obtained.

Example 18 2- (trans-2'-phenylvinyl) -1,3 instead of 2- (n-hexyl) -1,3-dioxolane
The same operation as in Example 6 was carried out except that 1.06 g of dioxolane was used, and 898 mg of a monoester of trans-cinnamic acid and ethylene glycol (yield: 77.9)
%)Obtained. ¹ H-NMR (CDCl ₃ ) δ 7.72 (d, 1 H, J = 15.9 Hz), 7.5
0 (m, 2H), 7.37 (m, 3H), 6.47
(D, 1H, J = 15.9 Hz), 4.35 (m, 2
H), 3.89 (m, 2H), 2.62 (brs, 1
^{H) IR (neat) 3444,1713,1638cm -1} MS (HRCI) m / z 192,0766 ( calcd 192,0786 as C ₁₁ H ₁₂ O ₃₎

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C07C 67/39 C07C 67/39 69/38 69/38 69/614 69/614 69/618 69/618 69/716 69/716 Z 69/78 69/78 69/92 69/92 253/30 253/30 255/19 255/19 // C07B 61/00 300 C07B 61/00 300 (56) References JP-A-56-118041 (JP , A) Takahiro Hosokawa a. Chem. Soc. , Chem. Commun. , 1983, p. 1245-1246 (58) Fields investigated (Int.Cl. ⁶ , DB name) C07C 69/28 C07C 67/39 C07C 69/38 C07C 69/614 C07C 69/618 C07C 69/716 C07C 69/78 C07C 69 / 92 CA (STN) REGISTRY (STN)

Claims (2)

(57) [Claims] 1. The general formula 1 (Wherein, R is a linear, branched or cyclic alkyl group having 1 to 15 carbon atoms; or a phenyl group, a phenyl lower alkyl group or a phenyl lower alkenyl group, wherein
Phenyl may have a lower alkyl group, a halogen atom, or a lower alkoxy group as a substituent. Or a lower alkyl group having a cyano group, a lower alkylcarbonyl group or a lower alkoxycarbonyl group as a substituent, and n represents 2, 3 or 4. A) reacting a cyclic acetal represented by the formula (1) with t-butyl hydroperoxide in the presence of a ruthenium catalyst; (Wherein, R and n have the same meanings as described above). 2. The method according to claim 1, wherein the ruthenium catalyst is ruthenium trichloride hydrate, dihydridotetrakis (triphenylphosphine).
The process for producing monoesters of diols according to claim 1, which is ruthenium, ruthenium dodecacarbonyl, ruthenium dichlorobis (2,2'-bipyridyl) or ruthenium dichlorotris (triphenylphosphine).