US3379770A - 3-alkoxycyclobutanols - Google Patents

3-alkoxycyclobutanols Download PDF

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US3379770A
US3379770A US414474A US41447464A US3379770A US 3379770 A US3379770 A US 3379770A US 414474 A US414474 A US 414474A US 41447464 A US41447464 A US 41447464A US 3379770 A US3379770 A US 3379770A
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alkoxycyclobutanols
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Edward U Elam
James C Martin
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Eastman Kodak Co
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups

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  • This invention relates to novel chemical compounds and their prepartion. More particularly, this invention relates to novel 3-alkoxycyclobutanols of the formula:
  • R --OHCH-OH a o- H- R R1 their preparation by the reduction of 3-alkoxycyclobutanones and to carboxylic acid esters of the 3-alkoxyclobutanols.
  • the substituent R can be hydrogen or lower alkyl and the substituent R is alkyl or aralkyl.
  • the substituents R and R when taken singly, are alkyl and, when taken collectively with the carbon atom to which they are attached, represent a saturated carbocyclic ring having 4 to 8 ring carbon atoms.
  • R when lower alkyl is typically alkyl of 1 to about 5 carbon atoms such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, etc.
  • R is typically substituted or unsubstituted alkyl of l to about 18 carbon atoms or aralkyl of 7 to about 19 carbon atoms and, when alkyl, is preferably alkyl of 1 to about 8 carbon atoms such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, etc.
  • R when aralkyl is typically benzyl, diphenylmethyl, triphenylmethyl, (p-tolyl)methyl, etc.
  • R and R when alkyl are typically alkyl of 1 to 18 carbon atoms and are preferably alkyl of 1 to about 8 carbons such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, pentyl,
  • R and R when taken collectively with the carbon atom to which they are attached to represent a saturated carbocyclic ring of 4 to 8 carbon atoms, typically represent carbocyclic rings such as cyclobutylidene, cyclopentylidene, cyclohexylidene, cycloheptylidene, and cyclooctylidene.
  • Examples of some of the preferred 3-alkoxycyclobutanols of our invention include compounds such as 2,2-dimethyl-3-methoxycyclobutanol; 2,2 dimethyl-3-ethoxycyclobutanol; 3 -benzyloxy-2,Z-dimethylcyclobutanol; 2- butyl-2-ethyl-3-butoxycyclobutano1; 2,2,4 trimethyl-3- ethoxycyclobutanol; 2,2 dimethyl-3-(2-ethylhexyloxy)- cyclobutanol; 1-ethoxy-3-hydroxyspiro[3.5] -nonane; 3- isobutoxy-Z,Z-dioctylcyclobutanol; 3-benzyloxy-4-ethy-l-2, Z-dimethylcyclobutanol; etc.
  • esters of our invention can be represented by the formulae:
  • R R R and R are as hereinbefore defined; R is the residue of an organic monocarboxylic acid and R is the residue of an organic dioic acid.
  • R typically has 1 to about 18 carbon atoms and preferably has 1 to about 8 carbon atoms.
  • monocarboxylic acid residues represented by R are those from alkanoic acids such as formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, etc.; unsaturated acids such as acrylic acid, methacrylic acid, oleic acid, etc.; substituted alkanoic acids such as trichloroacetic acid, etc.; and substituted or unsubstituted aromatic acids such as benzoic acid, p-nitrobenzoic acid, etc.
  • alkanoic acids such as formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, etc.
  • unsaturated acids such as acrylic acid, methacrylic acid, oleic acid, etc.
  • substituted alkanoic acids such as trichloroacetic acid, etc.
  • R typically has 1 to 18 carbon atoms and preferably contains 1 to about 8 carbon atoms.
  • diotic acid residues represented by R are those from acids such as carbonic acid and from organic dicarboxylic acids, e.g., alkanedioic, alkenedioic or arylenedioic acids, such as maleic acid, fumaric acid, succinic acid, adipic acid, phthalic acid, terephthalic acid, isophthalic acid, 3,3'-thiodipropionic acid; etc.
  • Examples of some of the preferred 3-alkoxycyclobutanol esters of our invention include compounds such as 3-ethoxy-2,Z-dimethylcyclobutyl acetate; bis(3-ethoxy-2, Z-dimethylcyclobutyl)adipate; 3 ethoxy-2,2-dimethylcyclobutyl decanoate; 3 methoxy-2,2-dimethylcyclobutyl benzoate; 3 ethoXy-2,2-dimethylcyclobutyl trichloroacetate; bis(3-ethoXy-2,Z-dimethylcyclobutyl)maleate; bis- (3-ethoxy-2,2-dimethylcyclobutyl fumarate; 3-butoxy-2,- 2 dimethylcyclobutyl ethylcarbonate; 3-methoxy-2,2dimethylcyclobutyl acetate; 3-ethoxy-2,Z-dimethylcyclobutyl p-nitrobenzoate; 3-isobutoxy 2,2
  • novel 3-alkoxycyclobutanols of our invention can be prepared by the reduction of a 3-alkoxycyclobutanone.
  • the latter compounds can be prepared by the cycloaddition of a ketoketene and an alkyl vinyl ether.
  • the reaction is carried out, e.g., by heating equimolar amounts of a ketoketene such as dimethyl ketene and an alkyl vinyl ether such as ethyl vinyl ether in an inert polar solvent as illustrated in Martin, US. patent application, Ser. No. 276,177, filed Apr. 29, 1963, and now Patent No. 3,312,- 741.
  • the reduction of the 3-alkoxycyclobutanone can be carried out chemically, i.e., with a chemical reducing agent, or catalytically by hydrogenation of the 3-alkoxycyclobutanone in the presence of a hydrogenation catalyst.
  • a boron containing chemical reducing agent such 'as an alkali metal borohydride, an alkoxyboro'hydride or an amineborane; with an alkali metal hydride such as lithium, sodium or potassium aluminum hydride or with an aluminum alkoxide such as aluminum isopropoxide.
  • a boron containing chemical reducing agent such 'as an alkali metal borohydride, an alkoxyboro'hydride or an amineborane
  • an alkali metal hydride such as lithium, sodium or potassium aluminum hydride or with an aluminum alkoxide such as aluminum isopropoxide.
  • chemical reducing agents are the 'alkali metal borohydrides, e.g., sodium borohydride.
  • the reduction is preferably carried out in an aqueous medium when an alkali metal borohydride is employed as the reducing agent.
  • Suitable catalysts include conventional supported and unsupported hydrogenation catalysts such as iron, nickel,
  • Nickel or ruthenium containing hydrogenation catalysts e.g., Raney nickel or supported ruthenium, are preferred.
  • the catalytic reduction of the 3-alkoxycyclobutanone is preferably carried out at elevated temperature and superatmospheric pressure, though temperatures as low as 25 C. and pressures as low as 1 atmosphere are suitable. Suitable temperatures and pressures are from about 25 C. to about 200 C. and about 1 atmosphere to about B00 atmospheres. Preferred temperatures are from about 50 C. to about 150 C. and preferred pressures are from about 10 to about 150 atmospheres.
  • Example 3 *0 H OH 1/4 NaBH4 CnHsO---J CH3 O HEO CH3 A solution of 30.5 g. (0.8 mole) of sodium borohydride in 300 ml. of water was stirred vigorously and treated with 280 g. of 2,2-dimethyl-3-ethoxycyclobutanone. 'An ice bath was used to keep the temperature below 50 C. during the addition. The mixture was stirred at room temperature overnight, and worked up as described in Example 1. The yield of 2,2-dimethyl-3-ethoxycyclobutanol, 'B.P. 97 C. (22 mm.), n 1.4460, was 223 g.
  • Example 4 -O Ru OH H I C2H5O CH3 CaHgO #011 H3 CH3
  • a solution of 250 ml. of 2,2-dimethyl-3-ethoxycyclobutanone in 250 ml. of ethyl alcohol was hydrogenated over 20 g. of 5% ruthenium on carbon at 75 C., 3000 p.s.i.
  • the product was filtered and dis-tilled to give 2,2-dimethyl3-ethoxycycldbutanol, BJP. 96-97 C. (22 mm.) in 60% yield.
  • Example '5 O N1 OH H CaH5O- CH3 02H) 3
  • a solution of ml. of 2,2-dimethyl-3-ethoxycyclobutanone in 75 ml. of ethanol was hydrogenated over 10 g. of 'Raney nickel at C., 3000 p.s.i.
  • the yield of 2,2-dimethyl-3-ethoxycyclobutanol, BxP. 97-98 (25 mm.) was 70%.
  • the 3-alkoxycyclobutanols of our invention are particularly useful as chemical intermediates, e.g., for the preparation of esters of 3-alkoxycyclobutanols.
  • the novel carboxylic acid esters, of the 3-alkoxycyclobutanols are prepared by conventional esterification methods.
  • the esterification can be carried out by contacting the 3-alkoxycyclobutanol with a carboxylic acid, an acid halide of a carboxylic acid or a carboxylic acid anhydride, preferably in the presence of an acidic or basic esterification catalyst.
  • a preferred method for preparing the novel esters of our invention is to contact the 3-alkoxycyclobutanol with an acid'halide, eg., an acid chloride, in the presence of a tertiary amine, e.g., pyridine.
  • an acid'halide e.g., an acid chloride
  • esters Another preferred method for the preparation of the esters is to contact the 3-alkoxycyclobutanol with the carboxylic acid in the presence of an aryl sulfonic acid, e.g., p-toluenesulfonic acid.
  • an aryl sulfonic acid e.g., p-toluenesulfonic acid.
  • Example 11 C1130 CH] A solution of 13 g. of 3-methoxy-2,Z-dimethylcyclobutanol in ml. of pyridine was treated with 15 g. of benzoyl chloride. The mixture was allowed to stand overnight, filtered from precipitated pyridine hydrochloride, and washed with water. The solvent was evaporated on the steam bath. The residue (23 g.) had n 1.5081. It was determined to be very pure by gas chromatography.
  • Example 12 Under the general conditions of Example 11, the following cyclobutanols and acid halides give the products shown:
  • cyclobutanol 500 ml. of benzene, 72 g. (1 mole) of acrylic 2 acid, 1 g. of hydroquinone monomethyl ether and 5 g. of p-toluenesulfonic acid was refluxed under a 6-in. Vigreux column equipped with a Dean-Stark water trap. After water removal was complete, the solution was washed with water, 10% sodium carbonate solution, water and dried over anhydrous sodium sulfate. This solution was distilled from cuprous chloride through a 6-in. Vigreux column to give 80.2 g. of 3-ethoxy-2,2-dimethylcyclobutyl acrylate, B.P. 80-83 C. (5 mm).
  • novel 3-alkoxycyclobutanols are useful, not only for the preparation of esters, but also as solvents, plasticizers, e.g., for vinyl resins, hydraulic fluids, etc.
  • the 3-alkoxycyclobutanol esters of unsaturated acids are useful in the preparation of copolymers with other unsaturated compounds and the 3-alkoxycyclobutanol esters with saturated car-boxylic acids are useful as plasticizers, solvents, etc.
  • Example 14 A plastic composition containing 66 parts of bis(2,2- dimethyl-3-eth0xycyclobutyl)adipate in polyvinyl chloride was prepared by milling the components together on heated rolls. The resulting plastic was tough, flexible and had good mechanical properties.
  • Example 15 A copolymer containing 3-ethoxy-2,2-dirnethy1- cyclobutyl acrylate and 70% acrylonitrile was prepared by conventional polymerization techniques. It had a sticking temperature of 160 C. and could be cast into tough films and spun into strong fibers.
  • R is selected from the group consisting of (a) hydrogen and (b) lower alkyl
  • R is selected from the group consisting of (a) alkyl of l-18 carbon atoms and (b) aralkyl of 7-19 carbon atoms;
  • R and R when taken singly, are alkyl of l-18 carbon atoms and, when taken collectively with the carbon atom to which they are attached, represent a saturated carbocyclic ring of 4 to 8 ring carbon atoms.

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Description

United States Patent 3,379,770 3-ALKOXYCYCLOBUTANOLS Edward U. Elam and James C. Martin, Kingsport, Tenn., assignors to Eastman Kodak Company, Rochester, N .Y-, a corporation of New Jersey No Drawing. Filed Nov. 27, 1964, Ser. No. 414,474 Claims. (Cl. 260-611) ABSTRACT OF THE DISCLOSURE The chemical or catalytic reduction of 3-alkoxycyclobutanones provide the corresponding 3-alkoxycyclobutanols. The 3-alkoxycyclobutanols are useful as chemical intermediates for example, in the preparation of carboxylic ester derivatives of the 3-alkoxycyclobutanols, as well as solvents, plasticizers, hydraulic fluids, etc.
DISCLOSURE This invention relates to novel chemical compounds and their prepartion. More particularly, this invention relates to novel 3-alkoxycyclobutanols of the formula:
R --OHCH-OH a o- H- R R1 their preparation by the reduction of 3-alkoxycyclobutanones and to carboxylic acid esters of the 3-alkoxyclobutanols.
In the above formula for the novel 3-alkoxycyclobutanols of our invention, the substituent R can be hydrogen or lower alkyl and the substituent R is alkyl or aralkyl. The substituents R and R when taken singly, are alkyl and, when taken collectively with the carbon atom to which they are attached, represent a saturated carbocyclic ring having 4 to 8 ring carbon atoms.
R when lower alkyl, is typically alkyl of 1 to about 5 carbon atoms such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, etc. R is typically substituted or unsubstituted alkyl of l to about 18 carbon atoms or aralkyl of 7 to about 19 carbon atoms and, when alkyl, is preferably alkyl of 1 to about 8 carbon atoms such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, etc. R when aralkyl, is typically benzyl, diphenylmethyl, triphenylmethyl, (p-tolyl)methyl, etc. R and R when alkyl, are typically alkyl of 1 to 18 carbon atoms and are preferably alkyl of 1 to about 8 carbons such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, pentyl,
hexyl, octyl, 2-ethylhexyl, etc. R and R when taken collectively with the carbon atom to which they are attached to represent a saturated carbocyclic ring of 4 to 8 carbon atoms, typically represent carbocyclic rings such as cyclobutylidene, cyclopentylidene, cyclohexylidene, cycloheptylidene, and cyclooctylidene.
Examples of some of the preferred 3-alkoxycyclobutanols of our invention include compounds such as 2,2-dimethyl-3-methoxycyclobutanol; 2,2 dimethyl-3-ethoxycyclobutanol; 3 -benzyloxy-2,Z-dimethylcyclobutanol; 2- butyl-2-ethyl-3-butoxycyclobutano1; 2,2,4 trimethyl-3- ethoxycyclobutanol; 2,2 dimethyl-3-(2-ethylhexyloxy)- cyclobutanol; 1-ethoxy-3-hydroxyspiro[3.5] -nonane; 3- isobutoxy-Z,Z-dioctylcyclobutanol; 3-benzyloxy-4-ethy-l-2, Z-dimethylcyclobutanol; etc.
The esters of our invention can be represented by the formulae:
wherein R R R and R are as hereinbefore defined; R is the residue of an organic monocarboxylic acid and R is the residue of an organic dioic acid.
R typically has 1 to about 18 carbon atoms and preferably has 1 to about 8 carbon atoms. Examples of monocarboxylic acid residues represented by R are those from alkanoic acids such as formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, etc.; unsaturated acids such as acrylic acid, methacrylic acid, oleic acid, etc.; substituted alkanoic acids such as trichloroacetic acid, etc.; and substituted or unsubstituted aromatic acids such as benzoic acid, p-nitrobenzoic acid, etc.
R typically has 1 to 18 carbon atoms and preferably contains 1 to about 8 carbon atoms. Examples of diotic acid residues represented by R are those from acids such as carbonic acid and from organic dicarboxylic acids, e.g., alkanedioic, alkenedioic or arylenedioic acids, such as maleic acid, fumaric acid, succinic acid, adipic acid, phthalic acid, terephthalic acid, isophthalic acid, 3,3'-thiodipropionic acid; etc.
Examples of some of the preferred 3-alkoxycyclobutanol esters of our invention include compounds such as 3-ethoxy-2,Z-dimethylcyclobutyl acetate; bis(3-ethoxy-2, Z-dimethylcyclobutyl)adipate; 3 ethoxy-2,2-dimethylcyclobutyl decanoate; 3 methoxy-2,2-dimethylcyclobutyl benzoate; 3 ethoXy-2,2-dimethylcyclobutyl trichloroacetate; bis(3-ethoXy-2,Z-dimethylcyclobutyl)maleate; bis- (3-ethoxy-2,2-dimethylcyclobutyl fumarate; 3-butoxy-2,- 2 dimethylcyclobutyl ethylcarbonate; 3-methoxy-2,2dimethylcyclobutyl acetate; 3-ethoxy-2,Z-dimethylcyclobutyl p-nitrobenzoate; 3-isobutoxy 2,2 dioctylcyclobutyl methacrylate; 3-ethoxy 2,2 dimethylcyclobutyl acrylate; 3-ethoxy 2,2 dimethylcyclobutyl oleate; bis(3-butoxy-2, Z-dimethylcyclobutyl)-3,3'-thiodipropionate; etc.
The novel 3-alkoxycyclobutanols of our invention can be prepared by the reduction of a 3-alkoxycyclobutanone. The latter compounds can be prepared by the cycloaddition of a ketoketene and an alkyl vinyl ether. The reaction is carried out, e.g., by heating equimolar amounts of a ketoketene such as dimethyl ketene and an alkyl vinyl ether such as ethyl vinyl ether in an inert polar solvent as illustrated in Martin, US. patent application, Ser. No. 276,177, filed Apr. 29, 1963, and now Patent No. 3,312,- 741.
The reduction of the 3-alkoxycyclobutanone can be carried out chemically, i.e., with a chemical reducing agent, or catalytically by hydrogenation of the 3-alkoxycyclobutanone in the presence of a hydrogenation catalyst.
When the reduction is carried out chemically, it is prefera'bly performed in a conventional manner with a boron containing chemical reducing agent such 'as an alkali metal borohydride, an alkoxyboro'hydride or an amineborane; with an alkali metal hydride such as lithium, sodium or potassium aluminum hydride or with an aluminum alkoxide such as aluminum isopropoxide. Especially preferred as chemical reducing agents are the 'alkali metal borohydrides, e.g., sodium borohydride. The reduction is preferably carried out in an aqueous medium when an alkali metal borohydride is employed as the reducing agent.
In operations of a commercial size, it is preferred to conduct the reduction of the 3-'allsoxycyclobutanone catalytically by contacting the 3-alkoxycyclobutanone with hydrogen in the presence of a hydrogenation catalyst. Suitable catalysts include conventional supported and unsupported hydrogenation catalysts such as iron, nickel,
cobalt, ruthenium, palladium, platinum, copper-chromium oxide, etc. Nickel or ruthenium containing hydrogenation catalysts, e.g., Raney nickel or supported ruthenium, are preferred.
The catalytic reduction of the 3-alkoxycyclobutanone is preferably carried out at elevated temperature and superatmospheric pressure, though temperatures as low as 25 C. and pressures as low as 1 atmosphere are suitable. Suitable temperatures and pressures are from about 25 C. to about 200 C. and about 1 atmosphere to about B00 atmospheres. Preferred temperatures are from about 50 C. to about 150 C. and preferred pressures are from about 10 to about 150 atmospheres.
The cfollowing examples illustrate the preparation of the novel compounds of our invention.
Example 1 1/4 NaBH; 0530 CH; onto CH3 (H; CH3
A solution of 200 g. of 2,2-dimethyl-3-methoxycyclobutanone in 300 ml. of methanol was hydrogenated over 20 g. of 5% ruthenium on carbon powder at 100 C., 3000 p.s.i. After reduction was complete, the product was filtered and distilled to give 158.1 g. (74% yield) of 2,2-dimethyl-3-rnethoxycyclobutanol, BJP. 95-96" C. (25 mm.), n 1.4470-1.4472.
Example 3 *0 H OH 1/4 NaBH4 CnHsO---J CH3 O HEO CH3 A solution of 30.5 g. (0.8 mole) of sodium borohydride in 300 ml. of water was stirred vigorously and treated with 280 g. of 2,2-dimethyl-3-ethoxycyclobutanone. 'An ice bath was used to keep the temperature below 50 C. during the addition. The mixture was stirred at room temperature overnight, and worked up as described in Example 1. The yield of 2,2-dimethyl-3-ethoxycyclobutanol, 'B.P. 97 C. (22 mm.), n 1.4460, was 223 g.
Example 4 -O Ru OH H: I C2H5O CH3 CaHgO #011 H3 CH3 A solution of 250 ml. of 2,2-dimethyl-3-ethoxycyclobutanone in 250 ml. of ethyl alcohol was hydrogenated over 20 g. of 5% ruthenium on carbon at 75 C., 3000 p.s.i. The product was filtered and dis-tilled to give 2,2-dimethyl3-ethoxycycldbutanol, BJP. 96-97 C. (22 mm.) in 60% yield.
Example '5 O N1 OH H: CaH5O- CH3 02H) 3 A solution of ml. of 2,2-dimethyl-3-ethoxycyclobutanone in 75 ml. of ethanol was hydrogenated over 10 g. of 'Raney nickel at C., 3000 p.s.i. The yield of 2,2-dimethyl-3-ethoxycyclobutanol, BxP. 97-98 (25 mm.) Was 70%.
Under the general conditions of Example 2, the following cyclobutanones are reduced to the corresponding 'cyclobutanols:
The 3-alkoxycyclobutanols of our invention are particularly useful as chemical intermediates, e.g., for the preparation of esters of 3-alkoxycyclobutanols. The novel carboxylic acid esters, of the 3-alkoxycyclobutanols are prepared by conventional esterification methods. The esterification can be carried out by contacting the 3-alkoxycyclobutanol with a carboxylic acid, an acid halide of a carboxylic acid or a carboxylic acid anhydride, preferably in the presence of an acidic or basic esterification catalyst. A preferred method for preparing the novel esters of our invention is to contact the 3-alkoxycyclobutanol with an acid'halide, eg., an acid chloride, in the presence of a tertiary amine, e.g., pyridine.
Another preferred method for the preparation of the esters is to contact the 3-alkoxycyclobutanol with the carboxylic acid in the presence of an aryl sulfonic acid, e.g., p-toluenesulfonic acid.
The following examples illustrate the preparation of the novel carboxylic acid esters of 3-alkoxycyclobutanols of our invention.
Example 8 CHtCOOH C|H|O CH:
I odont J 4* Hi CgHgO OH:
A mixture of 71 g. of 2,2-dimethyl-3-ethoxycyclobutaml, 100 ml. of acetic acid, 100 ml. of toluene, and 0.5 g. of p-toluenesulif onic acid was refluxed under a Dean-Stark trap until no {more water came over. The product was treated with 5 g. of potassium acetate and ;distilled to give 76 g. of 2,2-dimethyl-3-ethoxycyclobutyl acetate, B.P., 95-10l C.
Example 9 O (CHah 0:]-
6 Analysis.Ca1cd. for c m o Sapon. equiv., 198. Found: Sapou. equiv., 195.
Example 10 mil iC HI C IHLO i c H:
A mixture of 71 g. (0.5 mole) of 2,2-dimethyl-3-ethoxycyclobutanol, 103 g. (0.6 mole) of decanoic acid, ml. of toluene, and 2 g. of p-toluenesulfonic acid was refluxeld under a Dean-Stark trap until all of the water had been removed. The product was stripped of solvent and the residue distilled in acyclic falling film molecular still to give 2,2-dimethyl-3-ethoxycyclobutyl decanoate, B.P. 85 (70,), hp 1.4460.
Analysis.--Calcd. for C H O: Sapon. equiv., 298. Found: Sapon. equiv., 289.
Example 11 C1130 CH] A solution of 13 g. of 3-methoxy-2,Z-dimethylcyclobutanol in ml. of pyridine was treated with 15 g. of benzoyl chloride. The mixture was allowed to stand overnight, filtered from precipitated pyridine hydrochloride, and washed with water. The solvent was evaporated on the steam bath. The residue (23 g.) had n 1.5081. It was determined to be very pure by gas chromatography.
Example 12 Under the general conditions of Example 11, the following cyclobutanols and acid halides give the products shown:
Cyclobutanol Acid Halide Product 1? OH H 0 C C 01: l CltCCC] C1 n0-( a)i C: a):
ll OH (I? (I? OCCH=CHCO- ClC CH=CHC C1 J I CaHs s): J B (C :):(C :)z 01 H OH (I? w 0 C O CIHI ClC OCIH! i l- 4 o 5): 9 t):
II OH r0 C CH: l BrCCHa i CH|O-(CH3): CH|O. -(CHI)I ii 0H p cm) -ocno,
ClC-Q-NO: CI s 1): CaHuO o 0 ll OH H (CsHn) 0CC=CH1 CIC C=CH2 i CH; (CHfllCHO-(CaHn): CH: (CHI)ICHO Cyclobutanol Acid Halide Product i l OH O C CHICHI O 0 11 CaHnO CEBU-(CH3); C10 CHlCHISCHICHIG C1 (CH3): 2
ii OH OO(OHz)1CH CzHO----(CH3): CH;(CH!)7CH=CH(CH1)1COC1 CtHsO CH3)! (H) a 1 l CHI Example 13 OH 1 CHFCHCO OH --r CaHrO O:
i O CH=CH:
cyclobutanol, 500 ml. of benzene, 72 g. (1 mole) of acrylic 2 acid, 1 g. of hydroquinone monomethyl ether and 5 g. of p-toluenesulfonic acid was refluxed under a 6-in. Vigreux column equipped with a Dean-Stark water trap. After water removal was complete, the solution was washed with water, 10% sodium carbonate solution, water and dried over anhydrous sodium sulfate. This solution was distilled from cuprous chloride through a 6-in. Vigreux column to give 80.2 g. of 3-ethoxy-2,2-dimethylcyclobutyl acrylate, B.P. 80-83 C. (5 mm).
The novel 3-alkoxycyclobutanols are useful, not only for the preparation of esters, but also as solvents, plasticizers, e.g., for vinyl resins, hydraulic fluids, etc. The 3-alkoxycyclobutanol esters of unsaturated acids are useful in the preparation of copolymers with other unsaturated compounds and the 3-alkoxycyclobutanol esters with saturated car-boxylic acids are useful as plasticizers, solvents, etc.
The following example illustrates the use of one of the esters of our invention as a plasticizer for a vinyl halide resin.
Example 14 A plastic composition containing 66 parts of bis(2,2- dimethyl-3-eth0xycyclobutyl)adipate in polyvinyl chloride was prepared by milling the components together on heated rolls. The resulting plastic was tough, flexible and had good mechanical properties.
The following example illustrates the preparation of a copolymer containing one of the esters of our invention.
Example 15 A copolymer containing 3-ethoxy-2,2-dirnethy1- cyclobutyl acrylate and 70% acrylonitrile was prepared by conventional polymerization techniques. It had a sticking temperature of 160 C. and could be cast into tough films and spun into strong fibers.
Although the invention has been described in detail with particular reference to certain preferred embodiments thereof, variations and modifications can be eflected within the spirit and scope of the invention as described hereinbefore and as defined in the appended claims.
We claim:
1. A compound having the formula:
R -OH-CH-OH R O--CH- --rt wherein:
R is selected from the group consisting of (a) hydrogen and (b) lower alkyl;
R is selected from the group consisting of (a) alkyl of l-18 carbon atoms and (b) aralkyl of 7-19 carbon atoms;
R and R when taken singly, are alkyl of l-18 carbon atoms and, when taken collectively with the carbon atom to which they are attached, represent a saturated carbocyclic ring of 4 to 8 ring carbon atoms.
2. A compound having the formula References Cited UNITED STATES PATENTS 7/ 1954 Schlesinger 260-617 X 6/1965 Elam et al. 260-617 BERNARD HELFIN, Primary Examiner.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4252738A (en) * 1977-04-09 1981-02-24 Bayer Aktiengesellschaft 1,2-Halohydrincarboxylic acid esters and a process for their preparation
US5185459A (en) * 1988-03-30 1993-02-09 E. R. Squibb & Sons Inc. Bis protected (hydroxymethyl)cyclobutanols

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2683721A (en) * 1952-01-17 1954-07-13 Hermann I Schlesinger Method of reducing and hydrogenating chemical compounds by reacting with alkali metal borohydrides
US3190928A (en) * 1961-09-27 1965-06-22 Eastman Kodak Co Preparation of tetraalkylcyclo-butanediols

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2683721A (en) * 1952-01-17 1954-07-13 Hermann I Schlesinger Method of reducing and hydrogenating chemical compounds by reacting with alkali metal borohydrides
US3190928A (en) * 1961-09-27 1965-06-22 Eastman Kodak Co Preparation of tetraalkylcyclo-butanediols

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4252738A (en) * 1977-04-09 1981-02-24 Bayer Aktiengesellschaft 1,2-Halohydrincarboxylic acid esters and a process for their preparation
US5185459A (en) * 1988-03-30 1993-02-09 E. R. Squibb & Sons Inc. Bis protected (hydroxymethyl)cyclobutanols

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