DE1237086B - Process for the preparation of trihydric alcohols - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

int. Cl .:

German class:

C07C 31 /

C07c

Number: 1 237 086

File number: B 80400 IV b / 12 ο

Filing date: February 6, 1965

Opened on: March 23, 1967

The new compounds which can be prepared according to the invention are those represented by the general formula

R ₂ R ₃ R ₄

DZ " ¹ f Z" ¹ D

IxI \ s I ^ ^ _ rv>

I I I

X Y OH

in which Rj to Rs represent hydrogen atoms or hydrocarbon radicals provided that one, R2 or R3, is hydrogen and the other is hydrocarbon radical; X represents an - OROH radical when R _{2 is} a hydrocarbon radical and a hydroxyl radical when R _{2 is} a hydrogen atom; Y represents an - OROH radical when R _{3 is} a hydrocarbon radical and a hydroxyl radical when R3 is a hydrogen atom; R means a divalent hydrocarbon radical.

Preferably R is a straight or branched chain alkylene radical, e.g. B. dimethylene (- CH ₂ CH ₂ -) or propylene (- CH (CH ₃ ) CH ₂ -). Ri to R _{5 are} preferably hydrogen atoms or lower alkyl radicals having 1 to 6 carbon atoms per radical. Suitable alkyl substituents are, for example, methyl, ethyl, n-propyl, isopropyl, η-butyl, sec-butyl and tert-butyl radicals. Ri and R5 can complete a six-membered carbocyclic ring.

The new triols according to the present invention can be prepared by the reaction of a suitable epoxy alcohol, in which the epoxy and hydroxyl groups sit on adjacent carbon atoms, with a diol HO R OH in the presence of an acidic catalyst such as sulfuric acid or aluminum chloride or boron trifluoride. Boron trifluoride is preferably in the form of a Complex used with an ether or an alcohol. Triplets of the formula given above can by reaction of the diol with an epoxy alcohol of the form)

R2 R3

Ri

OH

in which the R groups have the above meaning.

Epoxy alcohols which can be used as starting materials are, for example, 3,4-epoxy-4-methylpentanol-2; Process for the production of trihydric alcohols

Applicant:

The British Petroleum Company Limited, London

Representative:
_{| 0} Dipl.-Chem. Dr. W. Koch, Dr.-Ing. R. Glawe

and Dipl.-Ing. K. Delfs, patent attorneys,

Hamburg-Großflottbek, Waitzstr. 12th

■ 5 named as inventor:

Gordon Foster, Sunbury on Thames, Middlesex
(Great Britain)

Claimed priority:

Great Britain March 2, 1964 (8632)

2,3-epoxy-4-methylpentanol-4; 3,4-epoxyhexanol-2; 2,3-epoxyhexanol-4; 2,3-epoxy-3-methylpentanol-4; 1,2-epoxy-2-ethylbutanol-3 and 2,3-epoxy-2-ethylbutanol-1. Many of the epoxy alcohols useful as starting materials in the present invention can be prepared according to the method described in German patent application B 74346 IV b / 12 ο will.

Examples of suitable diols with the epoxy alcohols can be implemented include ethylene glycol, diethylene glycol and other polyethylene glycols, 1,2- or 1,3-propanediol or polymethylene diols, z. B. 1,6-hexanediol.

The reaction between the epoxy alcohols and the diols can be carried out at room temperature but is preferably carried out at reduced temperatures in the range of 0 to 1O ⁰ C. Conveniently, the alcohol is added dropwise to the diol in the presence of the catalyst over a period of time while the temperature is in the desired range, e.g. B. by means of an ice bath. When the addition is complete, alkali is added to neutralize the catalyst and the mixture is distilled. The product triols can be obtained by distillation at reduced pressures.

The new triol compounds are useful in the manufacture of polyesters and polyurethanes, at

70 »520/436

the manufacture of nest reclaimers t'iii \ invlkunststoiie and as chemical intermediates

The erfindungsgeinaße method is through the The following examples are explained in more detail

Example I.

1.3 ml of boron π-fluoride etherate are added to 250 ml of Äthvlengheol and the mixture is stirred slowly in an ice hockey rink at 0 to 4 ° C. 50.1 g of 3,4-epoxy-4-methylpentanol-2 are added dropwise with constant stirring in the Verlaute 7ugeset of Λ5 hours to the mixture / the temperature being maintained at 0 to 4 C When the /us.it/ is completed t.. I will ml of water and 2 g of potassium \ ~. carbonate to the product mixture was added and the mixture is distilled at a pressure of 2 mm Hg.

5K.56 g of a distillate at 140 to 143 ° C water cover. viscous liquid over this: o a yield of 76.5 ",,. based on theory, dar, and NMR spectroscopy and cleavage nut Periodic acid confirmed that the product 4- (2-Hydro \ yatho \ v) -4-methylpentane-2,3-diol was

Example -

0.5 irl Hortrirluoridälherat are added to 100 ml Äthylenglveol is added and the mixture is poured into stirred in an ice bath at 0 to 3 C. P.s are slowly drop by drop with constant stirring in the Over a period of 4 hours, 20 g of 2.3-l: .po \ v, -4-methyl-pentanol-4 added while the temperature at 0 to 3 C is held when the addition is completed is. I ml of water and I g of potassium carbonate are added; s added to the product mixture and the mixture is distilled at a pressure of 2 mm Hg

Distilling at 141 to 146.5 "C 22.29 g of a Water-white, viscous liquid over and solidify turns into a white crystalline base. Mp 37 to 3X C This represents a yield of 72.5 "(p. Related aiii the theory, dar and NMR spectroscopy and cleavage with periodic acid confirmed, dal * the product 2- (2-Hvdro \ vatho \ v) -4-methyfpentane-3,4-diol was

Claims (1)

Claims 1. A process for the preparation \ on trihydric alcohols. thereby α eke η η / e ι ch net. ■ '<daIi an epovy alcohol of the formula
Rj Rt R; R. C C 'C- OH in which Ri to R, Wasseisoll atoms or monovalent Hydrocarbon radicals. preferably Mean CV to Ci.-Alkvlradikalische, provided that that one. R. and the other means a hydrogen atom, in the presence of an acidic one Catalyst with a Glvcol of the formula IK) -R-OH. in which R is a bivalent Hydrocarbon radical. preferably a - \ lk \ - lenradical. implemented in a known manner is to make compounds of formula 1 K ϊ Κι R, -—- ν --C - C ■ OH to form in which X is an -OR OH radical. when Rz is a monovalent hydrocarbon radical and a hydroxyl radical. when R ^ is a hydrogen atom and Y is a - (.) R OH radical. when R _{5 is} a monovalent carbon atom, and a Hulrox® radical when R: is a hydrogen atom. 2 'method according to claim 1, characterized. that the catalyst is sulfuric acid. Aluminum chloride or boron fluoride 3 The method according to claim 1, characterized in that that the Epowalkohol is under 3.4-Epo \ v-4-methylpentanol - 2.2.3 - Fpo \ v - 4-methylpentanol-4. 3,4-Fpo \ yhe \ anol-2, 2.3-F.poKyhe \ anol-4. 2.3 - Epoxy - 3 - methylpentanol -4. 1.2 - Epo \ v-2 - ethvibutanol - 3 and 2.3 - Epoxy - 2 - ethylbutanol-I is selected 4. The method according to claim 1, characterized in that that the diol is under ethylene glycol. Dialhylene glycol. Polyethylene glycols: 1,2- or 1,3-propanediol and polymethylene diols selected is. 5. The method according to claim I. characterized in that that the reaction temperature in the range 0 to H) C is maintained.