JPH04283540A - Production of diol monoesters - Google Patents

Abstract

PURPOSE:To obtain a diol monoester under mild condition without forming diester by reacting a cyclic acetal with t-butyl hydroperoxide in the presence of a ruthenium catalyst. CONSTITUTION:The objective compound of formula II is produced by reacting (A) a compound of formula I [R is 1-15C straight, branched or cyclic alkyl or phenyl, phenyl-lower-alkyl or phenyl-lower-alkenyl (the phenyl group may be substituted with alkyl, halogen or alkoxy) or lower alkyl substituted with CN, alkylcarbonyl, etc.; n is 2-4] with (B) t-butyl hydroperoxide in the presence of (C) a ruthenium catalyst (e.g. ruthenium trichloride hydrate, dihydride tetrakis(triphenylphosphine) ruthenium or dodecacarbonyl triruthenium) preferably at 20-50 deg.C.

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 monoesters of diols represented by the following general formula (2). The monoesters of the diols mentioned above are useful compounds used, for example, as monomers for polymers having plasticity. (European published patent EP31691
8-A2)

0002

[Prior Art] A well-known method for obtaining monoesters of diols is the coupling of carboxylic acids or their derivatives with diols, but a considerable proportion of diesters are produced in addition to the desired monoesters. Therefore, it cannot be said that it is an industrially advantageous manufacturing method. In addition, a method for oxidizing cyclic acetals (Can. J. Chem., 5
2, 3651 (1974)) and J. Chem. So
c. , Chem. Commun. ,1245,(198
3)) It is difficult to say that these methods are industrially advantageous because they require low temperatures and long reaction times.

0003

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for producing diol monoesters that solves the various problems mentioned above.

0004

[Means for Solving the Problems] In order to solve the above-mentioned problems, the present inventors conducted various studies and arrived at the present invention. That is, the present invention has the following general formula:

(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, lower alkylcarbonyl group or lower alkoxycarbonyl group as a substituent; n represents 2, 3 or 4; ) is reacted with t-butyl hydroperoxide in the presence of a ruthenium catalyst.

[0006]The present invention provides a method for producing diol monoesters represented by the formula (wherein R and n have the same meanings as above).

Examples of the cyclic acetal represented by the general formula 1 used as a raw material in the present invention include 2-methyl-1,3-dioxolane, 2-n-hexyl-1,3-dioxolane, and 2-n-hexyl-1,3-dioxolane. n-heptyl-1
, 3-dioxolane, 2-n-pentadecyl-1,3-
Dioxolane, 2-n-hexyl-1,3-dioxane, 2-n-hexyl-1,3-dioxepane, 2-isopropyl-1,3-dioxolane, 2-cyclohexyl-1,3-dioxolane, 2-phenyl- 1,3-dioxolane, 2-(4'-methoxyphenyl-1,3-dioxolane, 2-(3',4'-methylenedioxyphenyl)-1,3-dioxolane, 2-p-tolyl-1,
3-dioxolane, 2-(4'-ethylphenyl)-1
, 3-dioxolane, 2-(4'-chlorophenyl)-
1,3-dioxolane, 2-(4'-bromophenyl)
-1,3-dioxolane, 2-(3'-chlorophenyl)1,3-dioxolane, 2-phenyl-1,3-dioxane, 2-phenyl-1,3-dioxepane, 2-benzyl-1,3-dioxolane , 2-(4'-chlorobenzyl)-1,3-dioxolane, 2-(2'-oxopropyl)-1,3-dioxolane, 2-(2'-oxopropyl)-1,3-dioxane, 2 -methoxycarbonylmethyl-1,3-dioxolane, 2-ethoxycarbonylmethyl-1,3-dioxolane, 2-cyanomethyl-1,3-dioxolane, 2-cyanomethyl-1,
3-dioxane, 2-(1'-propenyl)-1,3-
Dioxolane, 2-(2'-phenylvinyl)-1,3
-dioxolane, 2-(2'-phenylvinyl)-1,
Examples include 3-dioxane.

Examples of the ruthenium catalyst include ruthenium trichloride hydrate, dihydridotelakis(triphenylphosphine)ruthenium, dodecacarbonyltriruthenium, dichlorobis(2,2'-bipyridyl)ruthenium or dichlorotris(triphenylphosphine)ruthenium. The amount used is not particularly limited, but
Usually, it is used in a 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 relative to the cyclic acetal.

[0009] In the present invention, a reaction solvent is not particularly required, but when a solvent is used, inert solvents such as benzene, monochlorobenzene, dichloromethane, etc. can be mentioned. The amount of solvent used is not particularly limited, but
It is usually used in an amount of 0.5 to 9 times the weight of the cyclic acetal.

The reaction temperature is generally in the range from 0°C to the reflux temperature of the reaction mixture, preferably in the range from 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 end point of the reaction may be defined as the point at which the cyclic acetal as a raw material disappears. Usually, 4 hours after completion of dripping.
The reaction reaches the end point in ~5 hours.

After completion of the reaction, for example, an aqueous solution of sodium sulfite is added to the reaction mixture and the remaining peroxide is decomposed by stirring, followed by separation, washing, concentration, and if necessary column chromatography to obtain the desired diol. monoesters can be obtained.

0012

Effects of the Invention The present invention is a method for reacting easily available t-butyl hydroperoxide and a cyclic acetal under mild conditions using a ruthenium complex that is low in toxicity and easy to prepare, and the reaction time is This is a short and excellent method for producing diol monoesters that does not produce diester forms.

[0013]

EXAMPLES The present invention will be explained in more detail with reference to Examples below, but the present invention is not limited thereto.

Examples 1 to 5 and Comparative Example 1 300 mg of 2-phenyl-1,3-dioxolane, 2-phenyl-1
, 3-dioxolane to a mixture of 3 mol % catalyst and 2.0 ml of benzene at 25°C.
0.56 ml of benzene solution of butyl hydroperoxide
was added dropwise over 1 hour. The reaction mixture was further stirred at the same temperature for 1 hour and then analyzed by GC to obtain the results shown in Table 1. The product (monoester of benzoic acid and ethylene glycol) was quantitatively determined by GC-IS method.

[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 7
5.3 51.5
Comparative example 1 None 0
．． 0 0.0──
──────────────────────────
──────Note) Cat-1: Ruthenium trichloride hydrate Cat-2: Dihydridotetrakis(triphenylphosphine)ruthenium Cat-3: Dodecacarbonyl triruthenium Cat-
4: Dichlorobis(2,2'-bipyridyl)ruthenium Cat-5: Dichlorotris(triphenylphosphine)ruthenium *1 vs. 2-phenyl-1,3-dioxolane *2
2-phenyl-1,3-dioxolane

[0016]
Example 6 2-(n-hexyl)-1,3-dioxolane 949m
g, ruthenium trichloride hydrate 47 mg and benzene 6
．． 5.07 ml of a benzene solution of 3.55 M t-butyl hydroperoxide was added dropwise to the 0 ml mixture at 25° C. over 1 hour. After stirring the reaction mixture for an additional 4 hours at the same temperature, a solution of the reaction mixture with ether added was passed through Florisil column chromatography and eluted with ether. The oil obtained by concentrating the ether solution under reduced pressure was purified by preparative thin layer chromatography to obtain 751 mg of a monoester of heptanoic acid and ethylene glycol (yield: 71.
9%) was obtained as a colorless oil. 1 H-NMR (CDCl3) δ 4.21 (m, 2H), 3.82 (m, 2H),
2.44 (m, 1H), 2.35 (t, 2H, J=7.
6Hz), 1.63 (m, 2H), 1.30 (m, 6H
), 0.89 (t, 3H, J=7.1Hz) IR(ne
at) 3460, 1738, 1173cm-1MS (HRCI
) m/z 175, 1334 (calculated value as C9 H18O3 175, 1334)

Example 7 The same procedure as in Example 6 was carried out except that 901 mg of 2-phenyl-1,3-dioxolane was used instead of 2-(n-hexyl)-1,3-dioxolane, and benzoic acid and ethylene 787 mg (yield 78.9%) of monoester with glycol was obtained as a colorless oil. 1H-NMR (CDCl3) δ 8.05 (m, 2H), 7.38-7.58 (m
, 3H), 4.44 (m, 2H), 3.93 (m, 2H)
), 2.59 (brs, 1H)) IR (neat) 3444, 1721, 1279cm-1MS (HRCI
) m/z 167,0714 (calculated value as C9 H10O3 167,0708)

Example 8 The same procedure 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. 944 mg (yield: 80.2%) of a monoester of p-methoxybenzoic acid and ethylene glycol was obtained as a pale yellow oil. 1 H-NMR (CDCl3) 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-1MS (HRCI
) m/z 197,0803 (calculated value as C10H13O4 197,0814)

Example 9 2-(p-tolyl)-1,3-dioxolane 985m instead of 2-(n-hexyl)-1,3-dioxolane
The same operation as in Example 6 was carried out except for using p-
927 mg (yield: 85.7%) of a monoester of methylbenzoic acid and ethylene glycol was obtained as a colorless oil. 1H-NMR (CDCl3) δ 7.94 (d, 2H, J=8.3Hz), 7.2
2(d, 2H, J=8.3Hz), 4.43(ddd,
2H, J=5.9Hz, 3.2Hz, 1.2Hz), 3
．． 93 (ddd, 2H, J=5.9Hz, 3.2Hz,
1.2Hz), 2.46(brs, 1H), 2.40(
s, 3H) IR (neat) 3439, 1715, 1281cm-1MS (HREI
) m/z 180,0798 (calculated value as C10H12O3 180,0786)

Example 10 The same procedure as in Example 6 except that 1.11 g of 2-(4'-chlorophenyl)-1,3-dioxolane was used instead of 2-(n-hexyl)-1,3-dioxolane. 1.05 g (yield: 87.1%) of a monoester of p-chlorobenzoic acid and ethylene glycol was obtained as a pale yellow oil. 1 H-NMR (CDCl3) 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, 1275cm-1MS (HRCI
) m/z 201, 0308 (C9 H10O3 Cl
Calculated value as 201,0318)

Example 11 The same procedure 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). 971 mg (yield 80.6%) of a monoester of m-chlorobenzoic acid and ethylene glycol was obtained as a pale yellow oil. 1 H-NMR (CDCl3) δ 8.02 (dd, 1H, J= 2.2Hz, 1.5
Hz), 7.93 (ddd, 1H, J=7.8Hz, 1
．． 5Hz, 1.2Hz), 7.53(ddd, 1H, J
=7.8Hz, 2.2Hz, 1.2Hz), 7.37(
t, 1H, J=7.8Hz), 4.46(m, 2H),
3.96 (m, 2H), 2.37 (brs, 1H) IR (neat) 3430, 1725, 1292, 1260cm-1MS
(HREI) m/z 200, 0218 (C9 H9 O3 Cl
Calculated value as 200, 0240)

Example 12 The same procedure 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
, 624 mg of monoester with 3-propanediol (
Yield: 57.7%) was obtained as a colorless oil. 1H-NMR (CDCl3) δ 8.03 (m, 2H), 7.54 (m, 1H),
7.43 (m, 1H), 4.49 (t, 2H, J=6.
1Hz), 3.78 (t, 2H, J=6.1Hz), 2
．． 25 (brs, 1H), 2.01 (tt, 2H, J=
6.1Hz) IR (neat) 3420, 1721, 1277cm-1MS (HRCI
) m/z 181,0865 (calculated value as C10H13O3 181,0865)

Example 13 The same procedure 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 and 1,4-butanediol monoester 539 mg (
Yield: 46.3%) was obtained as a pale yellow oil. 1H-NMR (CDCl3) δ 8.03 (m, 2H), 7.55 (m, 1H),
7.42 (m, 2H), 4.36 (t, 2H, J=6.
3Hz), 3.71 (t, 2H, J=6.6Hz), 1
．． 67-1.92 (m, 5H) IR (neat) 3416, 1719, 1277cm-1MS (HREI
) m/z 194,0950 (calculated value as C11H14O3 194,0943)

Example 14 The same procedure as in Example 6 was carried out except that 985 mg of 2-benzyl-1,3-dioxolane was used instead of 2-(n-hexyl)-1,3-dioxolane, and phenylacetic acid and ethylene 666 mg of monoester with glycol (
Yield: 61.6%) was obtained as a pale yellow oil. 1 H-NMR (CDCl3) δ 7.22-7.35 (m, 5H), 4.21 (m
, 2H), 3.77 (m, 2H), 3.66 (s, 2H
), 2.22 (brs, 1H) IR (neat) 3460, 1736, 1161cm-1MS (HRCI
) m/z 181,0870 (calculated value as C10H13O3 181,0865)

Example 15 The same procedure as in Example 6 was carried out except that 781 mg of 2-(2'-oxopropyl)-1,3-dioxolane was used instead of 2-(n-hexyl)-1,3-dioxolane. A monoester of acetoacetic acid and ethylene glycol is obtained.

Example 16 The same procedure 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. 333 mg (yield 31.5%) of a mixed ester of ethanol and ethylene glycol was obtained. 1 H-NMR (CDCl3) δ 4.30 (m, 2H), 4.22 (q, 2H, J
=7.3Hz), 3.83(m, 2H), 3.42(s
, 2H), 2.57 (brs, 1H), 1.29 (t,
3H, J=7.3Hz)) IR (neat) 3507, 1734 cm-1 MS (HRCI) m/z 177, 0757 (calculated value as C7 H13O5 177, 0763)

Example 17 679 mg of 2-cyanomethyl-1,3-dioxolane instead of 2-(n-hexyl)-1,3-dioxolane
A monoester of malonitrile and ethylene glycol is obtained by carrying out the same operation as in Example 6 except for using .

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 monoester of trans-cinnamic acid and ethylene glycol was obtained (yield 77.9%).
)Obtained. 1H-NMR (CDCl3) δ 7.72 (d, 1H, J=15.9Hz), 7.
50 (m, 2H), 7.37 (m, 3H), 6.47 (
d, 1H, J=15.9Hz), 4.35(m, 2H)
, 3.89 (m, 2H), 2.62 (brs, 1H) IR (neat) 3444, 1713, 1638cm-1MS (HRCI
) m/z 192,0766 (calculated value as C11H12O3 192,0786)

Claims (2)

[Claims] Claim 1: 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, lower alkylcarbonyl group or lower alkoxycarbonyl group as a substituent; n represents 2, 3 or 4; ) and t-butyl hydroperoxide in the presence of a ruthenium catalyst. A method for producing diol monoesters. [Claim 2] The ruthenium catalyst is ruthenium trichloride hydrate, dihydridotetrakis(triphenylphosphine)ruthenium, dodecacarbonyltriruthenium, dichlorobis(2,2'-bipyridyl)ruthenium or dichlorotris(triphenylphosphine)ruthenium. A method for producing diol monoesters according to claim 1.