Patented May 30, 1944 2,350,147

UNITED STATES PATENT OFFICE 2,350,147 TER PENEETHER Joseph N. Borglin, Wilmington, Del, assignor to Hercules Powder Company, Wilmington, Del, a corporation of Delaware No Drawing. Application July 29, 1942, Serial No. 452,798 19 Claims. (C. 260-611) This invention relates to a method for the pro ethoxyl content of 13.1%, or a terpene ether con duction of terpene ethers. More particularly it tent of 52.7%. , Eacample III relates to a method for the production of terpene ethers by the addition of an alcohol at a double Two hundred and seventy parts of alpha bond of an unsaturated terpene compound under pinene, sixty parts of ethylene glycol, and six the catalytic action of sulfamic acid. parts of sulfamic acid were refluxed for 70 hours The ethyl ether of camphene has been pro at a reflux temperature which reached a maxi duced heretofore by the reaction of ethyl alcohol mum of 186 C. The reaction, mixture, Was with the complex cyclic terpene camphene in the washed with water to remove the unreacted presence of sulfuric acid as a catalyst. Thus, O ethylene glycol and the water-washed reaction Semmler (Ber. 33, pp. 3420-32) produced such a mixture distilled at a final bath temperature of compound by boiling a mixture of camphene, 175 C. to remove the unreacted alpha-pinene. ethyl alcohol, and sulfuric acid under reflux for Analysis of the resulting product indicated a hy several hours. I. W. Humphrey in U. S. Patent droxyl content of 3.4% or a yield of terpene 2,136,011 found that organic sulfonic acids were 5 ethers equal to 57.8%. superior to sulfuric acid as catalysts for the ad The products in accordance with this inven dition of an alcohol at a double bond of an un tion are ethers produced by the addition of an saturated terpene compound. alcohol to an unsaturated terpene compound at Now in accordance with this invention it has a double bond of the terpene compound. When been found that sulfamic acid acts to catalyze 20 polyhydric alcohols are used, the ethers so pro the formation of terpene ethers by the addition duced may contain one or more unreacted hy of an alcohol at a double bond of an unsaturated droxyl groups derived from the polyhydric alco terpene compound in a manner superior to the hol or it may contain a hydroxyl group of the manner in which sulfuric acid and Organic sul 25 terpinic group carried over from the original. fonic acid operate. . . sterpene compound reacted. Alternately, the The method in accordance with this invention ethers produced may contain one terpene group comprises reacting an unsaturated terpene com and two groups derived from a polyhydric alcohol pound with an alcohol in the presence of sulfamic or may contain two or more terpinic groups -acid. The reaction produced by this method ap 30 linked by ether linkages to one hydrocarbon chain pears to involve the addition of the acid cat derived from a polyhydric alcohol. Again the alyst to a double bond of the unsaturated ter product may contain one terpinic group linked to pene, to produce an unstable intermediate com one hydrocarbon chain derived from a polyhydric pound which reacts with the alcohol to produce alcohol by two ether linkages. a terpene ether. 35 It will be understood that a great number. O The method in accordance with this invention ethers are produced by the combination of the is illustrated by the following specific examples, various polyhydric alcohols with the various un all parts being by weight unless otherwise saturated terpene compounds in the various ways specified: set forth in the examples and that all such com Eacample I 40 pounds are included in the scope of this inven tion. Such ethers will be termed 'additive' ter One hundred parts of alpha-pinene, two hun pene ethers to distinguish from ethers produced dred parts of methanol, and ten parts of sulfamic by reaction involving a hydroxyl group of a ter acid were refluxed at 75° C. for thirty hours. The pene alcohol. reaction mixture was then washed with water 45 In the production of “additive' terpene ethers . to remove unreacted methanol and any sulfamic by the reaction of an unsaturated terpene, with acid which might have dissolved. Analysis of an alcohol in accordance with the method of this the reaction product indicated a methoxyl con invention, the unsaturated terpene may be react tent of 14.2%, or an equivalent of 77.8% terpene ed with the alcohol to an extent such that the 50 product shows no unsaturated characteristics. ethers. Eacample II On the other hand, the product may show some unsaturation which may, if desired, be eliminated The conditions set forth in Example I were by contact with hydrogen in the presence of a duplicated except that 200 parts of ethanol were hydrogenation catalyst such as, for example, Analysisused in placeof the of reactionthe 200 productparts of showed methanol. an 55 platinum, palladium, nickel, etc. Thus, the hy 2 2,350,147 drogenation of unsaturated “additive' terpene terpene and the particular alcohol used and may ethers may be effected by contacting the ether be Varied over a range of about 30° C. to about with 2% of an active supported nickel hydrogena 200° C. From the standpoint of yield, reaction tion catalyst and hydrogen under a pressure of velocity and operating simplicity it is generally about 20 to about 250 atmospheres at a tempera preferable to maintain the temperature of the ture Within the range of about 75° C. to about reaction mixture within the range of about 75° 200° C. The terpene compound reacted by the C. to about 150° C. method in accordance with this invention may The time required for the reaction to take place be an unsaturated monocyclic terpene compound will also vary with the terpene compound and the Such as for example, dipentene, terpinene, ter 0. pinolene, or other unsaturated monocyclic ter alcohol used. It may Vary over a range of about pene alcohols or mixtures thereof; it may be an 5 hours to about 100 hours. But, in general, the unsaturated complex cyclic terpene capable of reaction takes place within 30-70 hours at ordi isomerization to an unsaturated monocyclic ter nary pressures. A lesser time is required when pene compound which may be, for example, al the reaction is carried out under pressure. pha-pinene, carene, etc., or it may be a bicyclic 5 The “additive' terpene ethers produced in ac terpene which is not readily isonerized under cordance with this invention are useful as sol the Conditions of the reaction such as for exan Wents and Softeners in coating compositions and ple, Inopinene, camphene, and bornylene. in printing inks. These terpene compounds need not be in the Fatentis:What I claim and desire to protect by Letters form of pure compounds to be treated in accord 20 ance With this invention, but may be reacted in 1. The method of producing an additive ter Crude forms. Thus, in place of the several pure pene ether which comprises reacting an alcohol terpene compounds, crude natural mixtures of with an unsaturated terpene compound in the terpene compounds as, for example, turpentine, presence of Sulfannic acid as catalyst. ,- 25 2. The method of producing an additiveter pine oil, etc., or mixtures of terpenes with pe pene ether which comprises reacting an alcohol troleum or other saturated hydrocarbons may be With a bicyclic terpene compound in the presence used. Various fractions from these mixtures may of Sulfanic acid as catalyst. also be used without the necessity of isolating the 3. The method of producing an additive ter compounds in their pure state, after the etheri 30 perae ether which comprises reacting an alcohol fication of a crude mixture of terpene compounds With a monocyclic terpene compound in the press or a mixture of terpene compounds. The prod ence of sulfamic acid as catalyst...... ucts may be separated from the unreacted com 4. The method of producing an additive ter ponents of the reaction mixture by fractional dis pene ether which comprises reacting monohydric tillation, by extraction with a selective solvent 35 for the ether or unreacted alcohol which is sub alcohol with a bicyclic terpene compound in the stantially immiscible with the reaction mixture, presence of Sulfamic acid as catalyst. or by combination of these methods. 5. The method of producing an additive ter The polyhydric alcohols used to produce the pene ether which comprises reacting polyhydric “additive” terpene ethers in accordance with this 4) alcohol With a bicyclic terpene compound in the invention may be, for example, ethylene glycol, presence of sulfanic acid as catalyst. propylene glycol, diglycol, trimethylene glycol, 6. The method of producing an additive ter glycerol, mannitol, sorbitol, pentaerytherite, etc. pene ether which comprises reacting methanol Monohydric alcohols such as, for example, methyl with a bicyclicterpene compound in the presence alcohol, ethyl alcohol, normal propyl alcohol, iso :45 -of sulfannic acid as catalyst. propyl alcohol, normal butyl alcohol, secondary 7. The method of producing an additive ter butylalcohol, amyl alcohol, ethylene, chlorohydrin, pene’ether which comprises reacting ethanol with tetrahydro-furfuryl alcohol, benzyl alcohol, lauryl a bicyclic terpene compound in the presence of alcohol, stearyl alcohol, oleyl alcohol, abietyl al 'Sulfanic acid as catalyst. cohol, pimarol, hydrogenated abietyl alcohol, hy 8. The method of producing an additive ter dropimarol, the mono-ethyl, mono-butyl, mono pene ether which comprises reacting an aliphatic methyl ether of polyhydric alcohols as ethylene glycol with a bicyclic terpene compound in the or diethylene glycol, etc., or mixtures thereof may presence of sulfamic acid as catalyst. - be reacted with terpene compounds, in accordance 9. The method of producing an additive: iter with the method of this invention, to produce "ad 5 pene ether which comprises reacting ethylene ditive' terpene ethers. glycol. With a bicyclic terpene compound in the The relative proportions of the alcohol and the presence of sulfarmic acid as catalyst. terpene compound used in the reaction mixture 10. The method of producing an additive ter will depend on the molecular weight of the alco pene ether which comprises reacting an alcohol hol. It is desirable to use not less than 1% mols, () With pinene in the presence of Sulfamic acid as and preferably at least, 3 mols of the aliphatic Catalyst. - alcohol per mol of the terpene compound. 11. The method of producing an additive ter The concentration of catalysts used in the re pene ether which comprises reacting monohydric action may be varied over a wide range. Thus, alcohol with pinene in the presence of sulfamic the amount of catalyst used calculated as Sul acid as catalyst. famic acid may be within the range of about 0.1% to about 25.0% of the weight of the alcohol con 12. The method of producing an additive ter tained in the reaction mixture. The preferred pene ether which comprises reacting polyhydric amount will depend on the particular alcohol and alcoholacid as catalyst.with pinene in the presence of sulfamic the particular terpene reacted. In general, how 70 ever, it is preferable to have the catalyst present 13. The method of producing an additive ter in amounts within the range of about 1% to about pene ether which comprises reacting methanol 10% by weight of the alcohol. - Withcatalyst. pinene in the presence of sulfamic acid as The temperature at which the reaction is car ried out will depend largely upon the particular 75 pene14. etherThe methodwhich comprises of producing reacting an additiveethanol withter 2,850,147 3 with alpha-pinene in the presence of Sulfamic pinene in the presence of sulfamic acid as cata acid as catalyst. lyst. 18. The method of producing an additive ter 15. The method of producing an additive ter pene ether which comprises reacting ethanol with pene ether which comprises reacting an aliphatic alpha-pinene in the presence of sulfanic acid as glycol with pinene in the presence of sulfamic catalyst. acid as catalyst. 19. The method of producing an additive ter 16. The method of producing an additive ter pene ether which comprises reacting ethylene pene ether which comprises reacting ethylene glycol with alpha-pinene in the presence of Sul glycol with pinene in the presence of sulfamic acid as catalyst. famic acid as catalyst. JOSEPEN. BORGN. 17. The method of producing an additive ter pene ether which comprises reacting methanol