JPS58198431A - Preparation of 2-alkoxy-alcohol - Google Patents

Abstract

PURPOSE:To prepare the titled compound, by reacting an acetal with CO and H2 under mild condition using a catalyst comprising Co (compound) and a metal (compound) selected from the I A, IIA, IIIA, IVA, VA, VIA, VB and VIB groups of the periodic table. CONSTITUTION:The titled substance is prepared by the reaction of an acetal of formula (R1-R3 are 1-6C alkyl or 7-12C aralkyl) with CO and H2 at 100- 250 deg.C under the partial pressure of CO and H2 of 5-200 atm in the presence of a catalyst composed of Co (compound) and a metal (compound) selected from the I A, IIA, IIIA, IVA, VA, VIA, VB and VIB groups of the periodic table (especially Li). The reaction is carried out in a solvent such as aromatic or aliphatic hydrocarbon, ether, organic acid ester, etc. EFFECT:The catalyst system prevents the production of by-products, and has remarkably elongated life. The separation and purification of the product is easy, and the energy can be saved.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing 2-flucoxy alcohol. More specifically, the present invention relates to a method of reacting carbon monoxide and hydrogen with 7-cetal to produce 2-flucoquino alcohol Yl1.

Conventionally, as a method for producing 2-flucoxy alcohol from synthesis gas and acetal, especially dimethyl acetal, the method described in U.S. Pat. No. 2,555,950 is known as a known method. However, this method
Despite the harsh conditions of hot water pressure (250°C, 850-950 atm), the reaction activity is low and the yield (4-15%) is low.

The inventors of the present invention have arrived at the present invention with the aim of overcoming the drawbacks of conventional methods (relaxing reaction conditions, improving reaction rate and yield).

That is, the present invention uses cobalt or cobalt compounds IA of the periodic table when producing 1tr2-flukoxy alcohol Vllll.
Group, IA*, Group IA, Group fVA, Group IA, Group IA, VB
Use of one or more metals selected from the group consisting of the group consisting of the group consisting of the group consisting of the group consisting of the group consisting of the group consisting of group V
-Production method of flufuxi alcohol [In the formula, R+, Rs and 8- represent an alkyl group having 1 to 6 carbon atoms, or a 1-ralkyl group having 7 to 12 carbon atoms, and may be tall- or different from each other. good,
] Although the detailed reaction mechanism of the prepared diagonal and hydrogen according to the present invention and l-setal is not clear, l! The combination reaction is expressed by the following chemical reaction formula) 1 凰 = Rs 0 (!l: HCHm OH 1 Rs OH and 7/or HOCHm HORI +R proverb OH Organic and inorganic cobalt compounds can be used as parto or cobalt compounds.For example, bases such as metal cobalt, cobalt octacarbonyl, fupartohydroccarbonyl, cobalt oxide, Mll cobalt, cobalt hydroxide, cobalt iodide, and basic cobalt carbonate. salt, copal acetate f,
f7f) Organic acid salts such as cobalt acid, chelate compounds such as cobalt bis-7ce-cobalt-cobalt, etc. are used.

In the present invention, in addition to cobalt or cobalt compounds, group IA, AM, IA, fVA, IA, and IA of the periodic table are used.
Group IA: lithium, sodium ■Group A: magnesium, calcium, strontium J
Valium [! : Yttrium fVAfj, titanium, zirconium, hafnium VAl
l! : vanadium, niobium, tantalum group IA nichrome, molybdenum, tungsten VB group = antimony VB group: tellurium, preferably 1 group: lithium, sodium group IA: barium ■ human group: yttrium ■ human group 2,000/, zirconium IA Group: vanadium Group IA: coombe, molybdenum, tungsten Group B: anti-sevenane Group 1B: tellurium, more preferably ■Al11. Lithium, sodium, mA group: barium, mA group: titanium, and IA group: lithium are particularly effective.

Incidentally, the metal or metal compound shadow lines mentioned above can be utilized in any and all types. For example, the metal itself, or in the form of crushed cedar metal, semi-metallic form - or carbonates, alides, hydroxides, saba, phosphates, phosphates, etc.
Halogen compounds, )l/compounds, thioshi/' compounds, sulfonates, C+-Cs lower alkokids such as methoxyd or methoxyd, noenokind, carboxyiono are cast from 1 to 20 carbon #8111i1f f-kano-toshi. metal carboxyl salt,
hydride, nitrite #I salt, sulfite, sonnite d+ji, 7
Cetyl 7) Edoa, sulfide, and Anonan, N'an, Ami 7,! Coordinated compounds such as amino acids or phenyl group, furkyl L+Or ・21h(J
, Li Mushroom CON , Li) IC
(Jj, LiCj.

Li*CrO42)1xO, Ll scmHsov
411sO, LiF.

L+*8iF@2HxO, LiHC(h・Hz(J,
LiUH.

Li0H0H*(J, LiI, Lil・3Hs
U, Li mushroom Cx0a.

L's(), Li JPOi,
Li5PO4・12H snow 0, Li out P
(JaLiCyH on, Li580i
, Li580i HmU.

LiH80a, Li, SOm, N
aCtHsUt, NaCrHsOtomi.

NaNHaHPO4・4H snow 0, NaCyHsOs
, NaBOm.

NaBUm・4 flea (to, Na13aUy, N
aBr, NaNaBr-2H.

NatCOs, NmwCOs・HtO, Na5HI
COih”2Ht(J.

NaHCOs, NaCj, NamC5HsOt
・2HtU.

Na*8mO* ・2HsO, NaOH, NaHCO etc.

Na11POa・6HtO, NaHtPO*4(tO,
NaI.

N1to2HsO, NaCsHsOm Nag8
tOs.

NaH80a・2HtO, NatMoOv, Nam
Cl0g.

NaH80a・HtO, NaBOs-HmO, NaH8
0a.

Na11zPOa・HzO, NaH80a *N
mxPL)4.

NaP (Jm, NaaPloy, NaH801
.

NaKC4H, (Ha・4H snow 0, Na
CyHsOx, NaJO4.

NaH80a, NaH80a, NaH80a
, Na1850m.

Mg(Cd(nut)y, MICIx, M,?
I proverb 0MMo.

M&(OH)m, Cm(CtHiO snow)嘗,
CaC0-, Ca1m.

Can, Cm<0H)t*8r(CaHs
OtJ*, 8rCU+.

8rIm, 8rO, 8r(OH)*
I Ba(CsHmU weight)t.

BaBr snow, BaC0n, BaC6yi
, Ba5xUs・2HxO.

Ba(OH)z13HzO, BaIz, BaU
, BaPOa.

HaSOx, 1JasO+, Yl (shi, Hμ) 2141
-1tU.

Y(OH)m, Yla, Y2O1,'
I'iBr, TiBrm.

TiBra, Ti(V meaning, TiCJi)
, TiCJ4, TiI*.

'I'iI recruitment, i'i Ia, Ti r
1ej04) J 10Hri0. TiO.

'l'th (lj, 'riU2. Ti0Hrz,
Ti(JC/!a, TiO[mushroom.

ZrBr2, ZrBr5, ZrBz
, Zr(:/2, 'lrc1m.

ZrCjt, ZrtO)()<, Zr
L, ZrI4, ZrUt.

Zr0C1t, Zr+8(c)2, HfBrx
,)IfCja.

)1f()x, VHrs, VBra
, VClz, VzUj.

NbBr1, NbCJ4, Nb1s, Nb
2 (Ja.

(:r((:tHm()2h, CrCjt
, Cr1x, Cr0a *Mo[”, 1
Jls, H*MoO*, MoC1j
, WOBz.

11zWaO+59Hz(J, HtW(Ji
, 8bHrt, 8bBrs.

8h1m, 8b2Ui, TeBrz
, 'reBr Snow 1*, Teas, etc. Of the metals or gold compounds, #! However, it is a preferred embodiment to use a @-state metal compound of an organic acid salt or oxide of acetic acid.

The amount of cobalt catalyst used in the present invention is based on the total volume of the reaction solution, 1jfi 0-001 to 10
j'-atom, preferably 0.005-5j' a
tom, more preferably 0.01 to 2#atom. Group IA of the periodic table used with cobalt catalysts,
IA group, 厘A group, ■A group, VA group, WA group, VB group and VB group σ+ metal or compound of said metal is cobalt 1y
It is used in the range of 0.01 to 1001-atoms, preferably 0.05 to 501-atoms, and preferably 0.1 to 201-atoms.

The amount used is usually 14 by straining the total volume of one reaction solution to a standard number.
7m 10-' to 501-atom, preferably 10
-4 to 20j'atom, more preferably 101 to 1
A range of 0#atoms is selected.

The reaction temperature for carrying out the method of the present invention is suitably in the range of, for example, 50 to 550°C, preferably 80 to 500°C, more preferably 100 to 250°C.7 The total reaction pressure is such that the reaction medium is in a liquid phase. - Sufficient to maintain carbon oxide and hydrogen at appropriate partial pressures. - Suitable partial pressures of chloride and hydrogen are 1 to 500 atm, optimal partial pressure is 3 to 500 atm, more optimal partial pressure is 5 to 200 atm, but wider than 0.05 to 1000 atm. Partial pressures within the atmospheric pressure range are also acceptable.

The stoichiometric ratio of carbon monoxide to hydrogen in the raw material gas in the above production reaction equation is 1:2. However, in actual records, the molar ratio of carbon monoxide to hydrogen has a much wider range, 1:1.
0G to 100:1, preferably 1:5U to 50:l, more preferably 1:10 to 10:IV can be used. - When the gas mixture is close to the chemical 111M ratio of oxidation element to hydrogen.

Since the worst result is obtained, the ratio of carbon monoxide to hydrogen is
A range of 1:0-5 to 1:5 is 411 times more preferable. Further, the carbon monoxide and water used in the present invention may be injected into the reaction zone individually, or may be introduced in the form of a mixture of -carbon oxide and hydrogen, so-called "synthesis gas".

Furthermore, these raw material gases do not necessarily have to be of high purity, and may contain carbon dioxide, methane, nitrogen, and rare gases. However, raw material gas of extremely low purity is undesirable because it increases the pressure of the reaction system.

Le! and Rs represent an alkyl group having 11 to 6 carbon atoms or a 7ralkyl group having 7 to 12 carbon atoms, and may be the same or different. Examples of such acecools include 7cetaldehyde dimethylethyl acetal, fuchionaldehyde dimethyl acetal, acetaldehyde dibutyl acetal, propionaldehyde diethyl, ruacetal, acetaldehyde methylethyl 7cetal,
Propionaldehyde methyl ethyl acetal, 7cetaldehyde dipropyl 7cetal, acetaldehyde dibutyl acetal, enyl 7cetaldehyde dimethyl acetal.

Tolylace) aldehyde dimethyl acetal can be mentioned.

In addition, 7-cetal can be produced using methods that are not derived from petroleum products such as basic raw material t ethylene, such as the reaction of methanol and synthesis gas (Japanese Patent Publication No. 48-2525, Japanese Patent Application Laid-Open No. 51-149).
213. Japanese Patent Publication No. 136110, 411-1972-
136111 etc.) or sieved from this.

Solvents used in the present invention include benzene, toluene,
Aromatic hydrocarbons such as xylene, mesitylene, trimethylbenzene, aliphatic hydrocarbons such as pentane, hexane, heptane, octane, ethers such as tetrahydrofuran, anisole, organic acid esters such as methyl acetate, ethyl acetate, methyl bupionate, etc. Can be mentioned.

In the method of the present invention, trivalent or trivalent organic phonetic compounds commonly used in analogous reactions are not used. Trivalent or trivalent organic nitrogen group compounds 11:111 have poor stability, and when they are used, it is necessary to add new organic nitrogen group compounds at regular intervals to prevent a decrease in activity, and they also produce by-products. A large amount of energy is required to separate and remove 1. That point.

The catalyst system of the present invention produces no by-products.

In addition to dramatically extending the life of the catalyst, it also facilitates product separation and purification, contributing to energy savings.

The method of the present invention can be suitably carried out in either batchwise or continuous reaction mode. The products and catalyst can be recovered from the reaction solution by known methods such as distillation.

Hereinafter, the present invention Vll#L will be explained with reference to Examples.
The present invention is not limited to the following examples.

Examples 1 to 16 Into a stainless steel 10-01117 capacity autoclave equipped with an electromagnetic rotary stirrer, a predetermined amount of 1.1-1 was added as shown in Table 1.
After charging dimethoxyethane, a catalyst, and solvent Y, and purging the inside of the suction crepe with nitrogen, hydrogen and carbon monoxide were injected at a predetermined pressure. After cooling the reactor, which was heated to a predetermined temperature shown in Table 1 and incubated for a predetermined time while stirring, the reaction solution was analyzed by gas chromatography. The results are shown in Table 2.

Example 17 An experiment was carried out in the same manner as in Example 1, except that 1,1-dimethoxypropane Yf was used instead of 1,1-dimethoxyethane. The experimental conditions are shown in Table 1.

The conversion rate of the raw material was 85.4%, the selectivity of the product 2-methoyac-butanol was 68.0%, and the production rate was 6.41 m
It was aj/j, Hr.

Comparison fl11-5 An experiment was conducted in the same manner as in Example 1, except that no promoter was used. The experimental conditions are shown in Table 1, and the results are shown in Table 2.

14-

Claims (1)

[Claims] (Al-Urea oxide and (BL water volume + C) formula, 7 cetal w of 0H8H1 reacted with 2
- When producing flufuxil alcohol r, cobalt or a cobalt compound is selected from the group η1 consisting of group IA, group A, XiaAl1k, NA group, VA group, human group, VBll, and B group of the periodic table. A method for producing a 2-alkoxy-alcohol using a metal or a compound of the metal having 1 or more carbon atoms (wherein) Ll, R1 and Rs are a fullal group having 1 to 6 carbon atoms, Alternatively, it represents an f-ral group having 7 to 12 carbon atoms, which may be the same or different from each other.]