DE1943532A1 - Process for the preparation of 2-halomethylpropane-1,3-diols, their monoethers and monoesters - Google Patents

Description

FARBENFABRIKEN BAYER AG

LEVERKU SE N-Beyerwerk GK / Bn Patent department

26th August 1969

Process for the preparation of 2-halomethyl propane-1,3-diols. their monoethers and monoesters

2-Halomethyl-propane-1,3-diols are known. To J. Barbiere and J. Matti, Bull. Soc. chim. 5, 1565 (1938) and after F.F. Glances and E.L. Schumann, Am. Chem. Soc. 76 3153 (1954), for example, 2-bromomethyl-2-methyl-propane-1,3-diol or 2-bromomethyl-2-ethyl-propane-1,3-diol from trimethylolethane or trimethylolpropane and 66 percent hydrobromic acid in a bomb tube or in one Present lemonade bottle in 28-48 percent yield. However, this procedure is technically uninteresting for on the one hand because of the low yields, on the other hand because the use of pressure vessels and one particularly high concentrated hydrobromic acid.

According to F. Andreas and G. Raue, J. Prakt. Chem. 36, 170 (1967) 2-chloromethyl-2-ethyl-propane-1,3-diol can be reacted of trimethylolpropane with thionyl chloride via the intermediate stage of the cyclic sulfite ester and subsequent Decomposition with hydrochloric acid with elimination of sulfur dioxide represent. Also this process for the production of 2-chloromethyl-propane-1,3-diol is for the technical Preparation of 2-halomethyl-propane-1,3-diols too expensive especially since the yield is only about 50 #.

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It has now been found, surprisingly, that 2-halomethyl-propane-1,3-diols can be used produce in a simple manner in excellent yields and with high purity can by reacting the corresponding oxetanes with concentrated hydrohalic acids.

With this method of operation, no pressure is applied and no or only a low external temperature supply is used the halomethyi-propane-1,3-diols directly in mostly Obtain crystallized form and only need to be separated from their mother liquors by known methods to become.

It is surprising that the reaction takes place even at room temperature or only slightly elevated temperature and with equivalents Run off amounts of hydrohalic acids. Furthermore, one could not expect the conversions to be complete run smoothly and without by-products, in particular that neither an "esterification of the free -CHpOH group occurs, nor that in the case of unsaturated carboxylic acid oxetanestera ester saponification or an addition to the Double bond takes place. Surprisingly, the crystalline end products are also obtained directly in almost all cases in high purity.

The present invention thus provides a process for preparing 2-halomethyl-propan-1 ₉ 3-DMEN, their mono ethers or Monoestern of the general formula

HaL-CH ₂ . CH ₂ OH

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R is hydrogen or an optionally substituted straight-chain or more branched. Alkyl or alkenyl radical or an optionally substituted aryl or aralkyl radical

is,
ο
R is an optionally substituted straight-chain or

branched alkyl or alkenyl radical or an optionally substituted aryl or aralkyl radical or -CH ₂ -0-R radical,
Hai stands for F, Cl, Br or J,

χ is -CO-, -CON-R ¹ or -SO ₉ -O- and

t ^ ₁

η = 0 or 1. R is preferably hydrogen or an optionally substituted straight-chain or branched C ₁ -C ₁₀ -AlCyI- or C ₀ -C (- alkenyl radical or an optionally substituted C 1 -C ₁ aryl radical or C ₇ -C ₁ ^ -

Aralkyl radical, R is preferably an optionally substituted straight-chain or branched C.-C ₁₂ -alkyl or C ₂ -Cg -alkenyl radical or an optionally substituted Cg-C ..- aryl radical or C ₇ -C ₁₁ -aralkyl radical and is

in addition -CH ₀ -OR ¹ .

- 1 ? The alkyl, alkenyl, aryl or aralkyl radicals R and R can, for example, by halogen atoms such as F, Cl, Br, I, by nitro groups, cyano groups, R -O groups, R -CO-O groups, (R ⁵ = C ₁ -Cg-AIlCyI-, Cg-C ^ aryl, C ₇ -C ₁ ^ aralkyl groups), R radicals (R ^ = C.-C ₁ ,, - alkyl or alkenyl radicals), OH- Groups may be substituted.

The process according to the invention is characterized in that one oxetanes of the general formula

C. O

R ² ^ ^X CH ₂ '

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1Θ 4353 Z

1P wherein R, R, X and η the abovementioned meaning, with hydrohalic acids, H-Hal, where Hal has the stated meaning, at temperatures between -20 and 120 °, preferably about 50 ° to about 100 ⁰ C, if appropriate in the presence of a polar solvent, optionally under pressure, is reacted. A polar solvent is preferably water.

As a starting material for the method according to the invention thus oxetanes of the general formula come

R ¹ (X) -O-CH ₉ CHp

in question in the

R is hydrogen or an optionally substituted one straight-chain or branched alkyl or alkenyl radical or an optionally substituted aryl or aralkyl radical is,

2
R is an optionally substituted straight-chain or

denotes branched alkyl or alkenyl radical or an optionally substituted aryl or aralkyl radical or CH ₂ -OR ¹ radical,

X denotes -CO-, -CON-R ¹ or -SO ₀ -O- and η = 0 or 1.

R is preferably hydrogen or an optionally substituted straight-chain or branched C ₁ -C ₁₂ -alkyl or Crj-Cg-alkenyl radical or an optionally substituted Cg-C ₁ -aryl radical or Cy-C ₁ [- aralkyl radical, R is preferably a optionally substituted straight-chain or branched C ₁ -C ₁₂ -AlkVl- or C ₂ -Cg-Alkenvlrest or an optionally substituted Cg-C ₁ Le A 12 457 - 4 -

1XD 9 8 1 0/2 2 9 4

194352?

Aryl radical or C ₇ -C _{1 R} aralkyl radical and is also -CH ₂ -O-R '.

1 2 The alkyl, alkenyl, aryl or aralkyl esters R and R can, for example, through halogen atoms such as F, Cl, Br, I, through nitro groups, cyano groups, R - ^ - O groups, R - CO-O groups , (R ⁵ = Cj-Cg-alkyl-, Cg-C ₁₀ -ATyI-, C ₇ -C ₁ ^ aralkyl groups), R ^ residues (R ⁴ = C ₁ -C ₁₂ -AUyI- or alkenyl residues), OH -Groups be substituted.

Oxetanes suitable for the process according to the invention are, for example:

3-methyl-3-phenoxymethyl-oxetane, 3-hydroxymethyl-3-phenoxymethyl-oxetane, S-phenoxymethyl ^ -p-tosyloxymethyl-oxetane, 3-ethyl-3-p-tolyloxymethyl-oxetane, 3-methyl-3- / 5-methyl-4-chloro-7-phenoxymethyl-oxetane, 3 ₅ 3-bisphenoxymethyl-oxetane, 3,3-bis-p-chlorophenoxymethyl-oxetane, 3,3-bis-2,4-dichlorophenoxymethyl-oxetane, 3,3- Bis-carbamyl-oxymethyl-oxetane, 3-phenoxy-3-carbamyloxymethyl-oxetane, 3-hydroxymethyl-3-dimethylaminomethyl-oxetane, 3-methyl-3-hydroxymethloxetane, 3-ethyl-3-hydroxymethyloxetane, acrylic acid, methacrylic acid and crotonic acid esters of 3-methyl-3-hydroxymethyloxetane and 3-ethyl-3-hydroxymethloxetane, the methyl, ethyl, phenyl and β-cyanoethyl ethers of 3-methyl-3-hydroxymethyl oxetane and 3-ethyl-3-hydroxymethyloxetane ; Also suitable are the urethanes of 3-ethyl-3-hydroxymethyl oxetane and 3-methyl-3-hydroxymethyloxetane, for example methyl, methoxymethyl, ethyl, propyl, butyl, allyl and phenyl -, p-Chlorophenyl, 3,4-dichlorophenyl, 4-nitrophenyl and cyclohexyl urethanes.

Particularly preferred oxetanes are those of the formula

^Y " ^CH

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2 \ /

C 0

Y-CH ₂ - "" ^X CH ₂ '

ORIGINAL INSPECTED

943522

in which Y represents Cl, Br, J and F or radicals -0 (X) _n -R ¹ (R ¹ has the meaning already given), as well as those of the formula

9 '

YC CH ₂

in which R, X, η have the meaning already given 2
and R represents Cj-Cg-alkyl radicals. 3-Ethyl-3-hydroxymethyl-oxetane and 3-methyl-3-hydroxymethyl-oxetane and their ethers (preferably cyanoethyl ether, methyl ether, ethyl ether and phenyl ether) and their esters with preferably acrylic acid, methacrylic acid and crotonic acid are particularly preferred.

The hydrohalic acids, water-free or in any concentration in dissolved form, for example between 2 fo and 70 #, used the commercially available aqueous concentrated hydrogen halide acids are preferably at a level from 30 to 60% of hydrogen halide _o Suitable solvents for the hydrogen halide acids are but ψ organic solvents, preferably lower alcohols such as methanol or ethanol, are also possible. The hydrohalic acids are used in a molar ratio of 1: 1 to about 1: 1.5, but preferably in a molar ratio of 1: 1.

The inventive process may at temperatures between -20 ° and 120 ⁰ C, preferably at temperatures of 20 ° to up to about 100 ⁰ C, carried out, where appropriate (preferably water) in a polar solvent or solvent-free, as far as one works with aqueous hydrohalic acids ( preferred method).
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ORIGIMALMNSPECTED 109810/2294

Polar solvents are e.g. methanol, ethanol, isopropanol, Acetone, dimethylformamide, tetrahydrofuran, dioxane, water is preferred.

The process can optionally be carried out using external pressure, for example up to 10 atmospheres, but preferably without pressure. For the continuous implementation, it is advisable to use a reactor which enables the required residence time and, if necessary, operates at temperatures above the melting point of the products to be expected so that they do not crystallize out in the reactor. The starting oxetanes can optionally contain up to 20 io water; anhydrous oxetanes are preferably used.

The order in which the reactants are added is irrelevant to the process according to the invention; so can for example the correspondingly built-up oxetane can be presented or the oxetane and the hydrohalic acid can be used at the same time feed into a suitable reactor or the hydrohalic acid is initially introduced and added the oxetane too. In the simplest case, a 48 percent commercial aqueous hydrobromic acid, for example, is used and the corresponding oxetane is added dropwise, the temperature rising to about 80 °. Then at about 90 ° stirred for a further one to four hours. It is then allowed to cool, expediently with stirring, the reaction product in most cases being crystalline in high yield and excellent purity is obtained and, for example, can be sucked off and dried directly from the mother liquor can.

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1943522

The compounds obtainable by the process according to the invention correspond to the general formula

R ¹ (X) _1n -O-CH ₉ CH ₉ OH \ /

IT ^x CH ₂ -HaI

1 2
in which R, R, X, η and Hal have the meaning given above. . - "

■ Of special interest are the compounds of the formula prepared by the novel method are

R ¹ -CO-O-CH ₀ CH ₀ OH ² \ / ²

- R CH ₂ -HaI.

-ι
where R represents an aliphatic unsaturated radical, for example the radical of acrylic, methacrylic or crotonic acid.

^ According to the present invention, it succeeds as new compounds 2-halomethylpropane-1,3-diol monoester, 2-halomethylpropane-1,3-diol monoether as well as 2-halomethylpropane-1,3-diol-monocarbamic acid ester to manufacture.

The present invention thus relates to 2-halopropane-1,3-diol monoesters the general formula

HO-CH _9v R ¹

C '

S \ 2

Hal-CH ₂ CH ₂ -O-CO-R

Lp A Ί? 4.57 - 8 -

10 9810/2294

R is an aliphatic saturated hydrocarbon radical

in one

with 1-6 carbon atoms and ρ
R is an aliphatic or unsaturated straight chain

branched C ^ -CLp hydrocarbon radical, the one or contains two olefinic double bonds and • Hal is F, Cl, Br, J.

In addition, are the subject of the present invention also 2-halomethyl-propane-1,3-diol monoether of the general one formula

HO-CH ₀ R ¹

Hal-CH / "^ CH ₀ -O-CH ₀ -CH ₀ -CN

in the

R is an aliphatic saturated C.-Cg hydrocarbon

rest and Hal is F, Cl, Br, J.

Finally, the present invention relates to 2-halomethyl-propane-1,3-diol monocarbamic acid esters general formula

HO-CH ₂ ^ R ¹

Hal-CH ₂ ^N CH ₂ -O-CO-NH-R ²

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1343532 10

in the

R is an aliphatic saturated C.-Cg hydrocarbon radical,

2
R is an aliphatic, cycloaliphatic ^ .araliphatic

or aromatic hydrocarbon radical with 1-7 carbon atoms, which can be substituted by Cl, Br, NO «, a CH ^ -O-CHp radical and
Hal F, Cl, Br, J are.

The compounds obtainable by the process according to the invention have technical interest in the production of polymers of various types according to the polyaddition or polycondensation process. The products are also of interest as intermediates for the manufacture of Plant protection products, pesticides and pharmaceutical preparations.

2-Halomethyl-propane-1,3-diols which can be prepared according to the invention the general formula

HO-CH ₉ CH ₀ -OH

2 _Nc / 2

₂ / \ ■

R. . CH ₂ -HaI

in which Hai and R ^{2 have} the meaning already given, are particularly suitable as chain extenders in the production of polyurethanes and give them a flame-retardant effect. Polyurethanes are produced in a manner known per se by reacting polyisocyanates with compounds having reactive hydrogen atoms with a molecular weight of 500-10,000, preferably 1000-5000, and the 2-halogen-

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methylpropane-1,3-diols as chain extenders. As polyisocyanates Any kind of such can be used, e.g. aliphatic, cycloaliphatic, aromatic and araliphatic Polyisocyanates, particularly preferred are 4 »4'-diphenylmethane diisocyanate, Tolylene 2,4- and 2,6-diisocyanate or mixtures of these isomers, hexamethylene diisocyanate, while as compounds with reactive Hydrogen atoms, in particular the higher molecular weight polyesters and polyethers known per se, come into consideration. The flame-retardant effect of the 2-halomethyl-propane-1,3-diols obtainable according to the invention is illustrated using an exemplary embodiment shown.

The present invention therefore also relates to the use of 2-halomethyl-propane-1,3-diols general formula

V CH ₂ -OH
C ^

CH ₂ -HaI

in the

ο
R is an optionally substituted straight-chain or branched alkyl or alkenyl radical or an optionally substituted aryl or aralkyl radical or a radical -CH ₅ -OR,

R is hydrogen or an optionally substituted straight-chain or branched alkyl or alkenyl radical or an optionally substituted aryl or aralkyl radical is and

ρ Hai stands for F, Cl, Br or J. Preferably R is a

optionally substituted straight or branched C ₁ -C ₁₂ or C ₂ -AIlCyI- -CG-alkenyl or an optionally substituted C ^ -C ₁ aryl or C ₇ -C ₁₁ - Ie A 12 457 - ^11-4 I ^

109810/2294

η 1

Aralkyl radical. R can also have the meaning -CH ₂ -OR, in which case R is preferably an optionally substituted straight-chain branched C ^ - ^c i 2 "" alkyl or Cp-Cg-alkenyl- or an optionally substituted Cg-C .-- Is aryl or C ₇ -C ₁ [- aralkyl radical.

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Example 1:

116 g (1 mol) of 3-ethyl-3-hydroxymethyl-oxetane are added dropwise to 222 g (1.1 mol) of 40 percent strength aqueous hydrobromic acid at room temperature over the course of one hour. The temperature rises under illumination of the reaction mixture to about 60 ⁰ C. It is stirred for 3 hours at 90 ⁰ C after allowed to cool and sucks the crystallized 2-ethyl-2-propan-brominethyl

1,3-diol after acid-free washing with a little ice water. After drying, 179 g, 91 % of theory with a melting point of 80-81 ° C. are obtained.

Example 2:

An analogous to the above experiment carried out with 168 g (1 mole) of 48 percent hydrobromic acid provides 90% 2-ithyl 2-bromomethyl-propan-1,3-diol with a melting point of 81-82 ⁰ C.

Example 3:

168 g (1 mol) of 48 percent strength aqueous hydrobromic acid are added dropwise to 116 g (1 mol) of 3-ethyl-3-hydroxymethyl-oxetane at room temperature. The temperature of the reaction mixture rises to about 60 ⁰ C. The mixture is stirred for four hours at 90 ⁰ C and after obtained analogously 190 g (96 # of theory) of 2-ethyl-2-bromomethyl-propan-1,3-diol with a melting point of 81-82 ⁰ C (recrystallized from water).

Example 4:

To 1 mole of 36.5 percent aqueous hydrochloric acid are added dropwise at room temperature over 15 minutes, 116g (1 mole) of 3-lthyl-3-hydroxymethyl-oxetane, whereby the temperature rises to about-90 ⁰ C. The mixture is stirred for four hours at 90 ⁰ C after allowed to cool and sucks, after washing with a little ice water containing 2-ethyl-2-chloromethyl-1,3-diol from. 138 g (91 # of theory) with a melting point of 63-64 ° C. are obtained. The product can be distilled without decomposition at 120-121 ° / 1 Torr. Ie A 12 457 - 13 -

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1943 522 Vt

Example 5:

To 450 g (2 moles) of 57 percent aqueous hydriodic acid are added dropwise at room temperature over 20 minutes 232 g (2 mol) of 3 ^ thyl-3-hydroxymethyl-oxetane, whereby the temperature rises to about 85 ⁰ C. The free iodine (from the hydriodic acid) is reduced with a little 10 percent solution of sulfur dioxide in dioxane; the reaction mixture becomes completely colorless. It is stirred for four hours at about 9O ⁰ C to, allowed to cool and sucks the crystalline 2-ethyl-2-jodmethylpropan-1,3-diol from. After | Washing with a little ice water and drying, 450 g is obtained (92 fo of theory) of melting point 79-80 ⁰ C.

Example 6; ·

51 g (0.5 mol) of 3-methyl-3-hydroxymethyloxetane are added to 0.5 mol of 36.5 percent strength aqueous hydrochloric acid at room temperature. The reaction mixture heats up to about 75 ° C. during the dropwise addition; the mixture is stirred for a further three hours at 90 ^° C., allowed to cool and the 2-methyl-2-chloromethyl-propane-1,3-diol is sharply suctioned off. Are thus obtained 105 g (75% of theory) of melting point 78 --- 80 ⁰ C.

Example 7;

W 51 g (0.5 mol) of 3-methyl-3-hydroxymethyl-oxetane are added dropwise to 84 g (0.5 mol) of 48 percent strength aqueous hydrobromic acid at room temperature. After three hours of subsequent reaction (about 9O ⁰ C) is allowed to cool overnight and forwards by grinding a crystallization. The crystals are filtered off with suction, washed with a little ice water and dried. This gives 64 g (71 # of theory) of 2-methyl-2-brommethylpropan-1,3-diol with a melting point of 71-72 ⁰ C (from water).

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Example 8:

Analogously to Example 7, using 56.3 g of 57 percent strength aqueous hydriodic acid and 25 »5 g (0.25 mol) of 3-methyl-3-hydroxymethyl-oxetane, 45 g (78 % of theory) of 2-Me" are obtained. thyl-2-iodomethyl-1,3-diol with a melting point of 81-82 ⁰ C.

Example 9:

56 ml of 48 percent strength aqueous hydrobromic acid are added dropwise to 85 g (0.5 mol) of acrylic acid ester of 3-ethyl-3-hydroxymethyl-oxetane at room temperature with stirring. The temperature rises to about 45 ^° C .; The mixture is stirred for four hours at 5O ⁰ C to the organic phase neutralized by washing with sodium bicarbonate solution and distilled to Monoacrylsäureester of 2-ethyl-2-bromomethyl-propan-1,3-diol in high vacuum. 99.5 g (80% of theory) of the boiling point at _{Q Q} ^ Torr 109 ° C. are obtained

Example 10;

26 g (0.2 mol) of 3-ethyl-3-hydroxymethyl-oxetane monomethyl ether are added dropwise to 33.4 g of 48 percent aqueous hydrobromic acid at room temperature with stirring. After the exothermic reaction is still about holding three hours at 85 ⁰ C, the organic phase is separated off and distilled 2-ethyl-2-bromomethyl-1,3-diol monomethyl ether in a water jet vacuum. 28 g (67 % of theory) are obtained from the boiling point at., ^ Torr 109-11O ⁰ C.

The 3-ethyl-3-hydroxymethyl-oxetane monomethyl ether is obtained by etherification of 3-ethyl-3-hydroxymethyl-oxetane with dimethyl sulfate.

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Example 11;

Dissolve 12.2 g (0.05 mol) of 3-ethyl-3-hydroxymethyl-oxetanp-chlorphenylurethan in 50 ml of dioxane and dropwise 6 ml of 48 percent aqueous hydrobromic acid, keeping for two hours at about 65 ⁰ C and pulls the Dioxane. This gives 12.5 g (76 io of theory) of 2-lthyl 2-bromomethyl-propan-1,3-diol (mono-p-chlorophenyl) urethane of melting point 85-87 ⁰ C.

The 3-ethyl-3-hydroxymethyl-oxetane-p-chlorphenylurethan of melting point 124-125 ⁰ C is obtained in known manner from p-chlorophenyl isocyanate and 3-ethyl-3-hydroxymethyl oxetane ^ in benzene in 95% yield.

Example 12:

12 ml of 48 percent hydrobromic acid are added dropwise to 17 g (0.1 mol) of 3-ethyl-3-hydroxymethyl-oxetane-β-cyanoethyl ether at room temperature with stirring. After the exothermic reaction is kept for four hours at 8O ⁰ C, cooled, neutralized and extracted with chloroform. The dried 2-ethyl-2-bromomethylpropane-1,3-diol-ß-cyanoethyl ether freed from chloroform is distilled on the oil pump. This gives 18 g (72 fo of theory) of boiling point at _{Q 2} Torr 134-135 ⁰ C. The product is analytically by gas chromatography, as well as uniform and spektros- w Kopisch secured.

3-ethyl-3-hydroxymethyl-oxetane-β-cyanoethyl-ether is obtained in good yields by adding acrylonitrile to 3-ethyl-3-hydroxymethy1oxetane in the presence of aqueous sodium hydroxide solution. Boiling point at _{n Λ} Torr 88 ⁰ C.

υ, ι

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Example 13:

15.8 g (0.1 mol) of 3-amyl-3-hydroxymethyloxetane are added dropwise to 0.1 mol of 48 percent hydrobromic acid at room temperature. The temperature of the reaction mixture rises to approx. 60 ^° C. during this process. The mixture is stirred for a further four hours at 90 ^° C.
neutralizes and washes the separated oil. After drying on a high vacuum pump, 20.9 g of 88% are obtained
Theory of 2-amyl-2-bromomethyl-propane-1,3-diol with a refractive index n £ ° = 1.4946.

Oxygen analysis: calculated: 13.38 ■ $>

found: $ 13.40>

The 3-amyl-3-hydroxymethyl-oxetane is obtained in 84 percent yield by reacting 1,1,1-trishydroxymethylhexane with diethyl carbonate in the presence of traces of potassium carbonate. Boiling point at 17 torr 148 - 149 ⁰ C,

20th
Refractive index n _D = 1.4555.

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Example 14:

Flame-retardant effect of 2-halomethyl-propane-1,3-diols:

Some diols were used to demonstrate the flame retardant effect incorporated as a chain extender in polyurethane elastomers. Compared to known 1,4-butanediol containing The 2-halomethyl-propane-1,3-diols produced according to the invention give elastomers their hardness as well as the Freezing temperature lowered, which is technically very desirable.

The products obtained are when tested according to ASTM D-635 self-extinguishing.

Manufacture of the polyurethanes:

a) 200 g of adipic acid-ethylene glycol polyester of molecular weight 2,000 were dehydrated at 130 ⁰ C in a vacuum and stirred for 30 minutes at 135 ° C with 80 g of 4,4'-diphenylmethane diisocyanate. 29 g of 2-chloromethyl-2-ethylpropane-1,3-diol (preparation according to Example 4) are added to the melt. After 60 seconds, the homogeneous melt is poured out and post-heated at 100 ^° C. for 20 hours. The result is an almost colorless * clearly translucent, tear-resistant elastomer sheet which does not harden at room temperature (Shore A 56).

5 samples tested according to ASTM D-635 were all found to be as self-extinguishing.

b) The same result is obtained when using 26.4 g of 2-chloromethyl- 2-methyl-propane-1,3-diol (preparation according to Example 6).

c) The procedure is as under a) but using 100 g of the diisocyanate and 51 »2 g of 2-bromomethyl-2-ethylpropane-1,3-diol (preparation according to Example 1 ) .

- ¹⁸ - ""«™" INSPECTBD

109810/22 94

1943522

The elastomer sheet obtained is hardly inflammable (Ignition only after 2 flame applications according to ASTM D-635). Out of 5 samples, 3 were self-extinguishing. The specimens do not harden at room temperature (Shore A 61).

ORIGINAL INSPECTED

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1 0 9 G. ' ° ^; · ■ / 9 4

Claims (11)

Patent claims: 1y process for the preparation of 2-halomethyl-propane-1,3-diols, their monoethers or monoesters of the general formula ¹ CH ₉ -OH CH ₂ -HaI wherein ~ R is hydrogen or an optionally substituted one ™ straight-chain or branched alkyl or alkenyl radical or an optionally substituted aryl or ar- alkyl radical,
2
R is an optionally substituted straight-chain or branched alkyl or alkenyl radical or an optionally substituted aryl or aralkyl radical or a -CH ₂ -OR ¹ radical and
Hai stands for F, Cl, Br or J,
x '= -CO-, -CO-N ^ ¹¹ or -SO ₂ -O- and η means 0 or 1, characterized in that one oxetanes of the general formula R ¹ - (X) _n -O-CH 1 2
where R, R, X and η have the meaning given above, with hydrogen halide acids H-Hal at temperatures between -20 ° and 120 ° C. 2. Embodiment according to claim 1, characterized in that that one for optionally dissolved in organic solvents, optionally containing up to 20 $ water Le A 12 457 - 20 - 10981 0 / 229.4 ORIGINAL INSPEGTEO 1943522 Zi Oxetane an at least 30 percent aqueous solution of the hydrohalic acid is added and the crystallized Separates reaction product and dries. 3. Embodiment according to claim 1, characterized in that the dissolved optionally in an organic solvent, optionally adding to an at least 30-percent aqueous solution of the hydrohalogenic acid containing up to 20 $> Water oxetane. 4. Embodiment according to claim 1, characterized in that the oxetane, optionally containing up to 20 fo water, and the at least 30 percent aqueous solution of the hydrohalic acid are fed simultaneously into a reactor. 5. Embodiment according to claim 1-4, characterized in that the reaction, starting at room temperature, with or without external heat input. 6. The method according to claim 1-5, characterized in that the oxetane and 3-methyl-3-hydroxymethyl-oxetane 3-A * ethyl-3-hydroxymethyl-oxetane is used. 7. The method according to claim 1-5, characterized in that the oxetane is the acrylic, methacrylic or crotonic acid ester of 3-ethyl-3-hydroxymethyl-oxetane or 3-methyl-3-hydroxymethyloxetane is used. 8. 2-halomethyl-propane-1,3-diol monoesters of the general formula HO-CH _{2 χ} R ¹ Hal-CH ₂ "CH ₂ -O-CO-R ² Le A 12 457 - 21 - ORIGINAL INSPECTED 109810/2294 1943Ü32 in the R is an aliphatic saturated hydrocarbon radical with 1-6 carbon atoms and
ρ R is an aliphatic unsaturated straight or branched chain C.-C. «-Carbon residue, the one or two contains olefinic double bonds, and Hal F, Cl, Br, J is. 9. 2-halomethyl-propane-1,3-diol monoether of the general formula HO-CHo R ¹ ₂ CH ₂ -O-CH ₂ -CH ₂ -CN in the R is an aliphatic saturated C -Cg hydrocarbon rest and
Hal F, Cl, Br, J is. 10. 2-Halomethyl-propane-1,3-diol monocarbamic acid ester the general formula · HO-CH ₂ .R ¹ C Hal-CH ₂ ^ CH ₂ -O-CO-NH-R ² in the R ^{1 is} an aliphatic saturated C ^ C ₆ hydrocarbon radical , R ^{2 is} an aliphatic, cycloaliphatic, araliphatic or aromatic hydrocarbon radical with 1-7 carbon atoms, which are substituted by Cl, Br, NO ₂ Le A 12 457 - 22 - 10 9 8 10/2294 ORiG ^ AL inspected can, a CH ^ -O-CHp radical and
Hal F, Cl, Br, J are. 11. Use of 2-halomethyl-propane-i, 3-diols of the general formula HO-CH ₀ CH ₀ -OH CH ₂ -HaI in the 2
R is an optionally substituted straight-chain or branched alkyl or alkenyl radical or an optionally substituted aryl or aralkyl radical or a radical -CH ₂ -O-R ¹ (R ¹ = hydrogen or an optionally substituted straight-chain or branched alkyl or alkenyl radical or an optionally substituted one Aryl or aralkyl radical) and Hal stands for F, Cl, Br or J, as a chain extender in the manufacture of polyurethanes from polyisocyanates and compounds with reactive hydrogen atoms. Le A 12 457 - 23 - 109810/2294