Патент USA US2136000код для вставки
2,130,000 ‘Patented Nov. 8, 1938 S. PATENT _ UNITED‘ STATE 2,136,000 OFFICE TERPENE ALCOHOL ESTERS or DIBASIC _ 'ACIDS AND METHOD OF PRODUCING Joseph N. Borgliu, Wilmington, DeL, assignor to Hercules Powder Company, Wilmington, Del., a corporation of Delaware 1 , No Drawing. Application December 18, 1934, Serial No. 758,033 9 Claims. (01. 260-99) This invention relates to terpene esters of di basic acids and methodfor their production. 'Heretoiore it has been known to esterify terpene alcohols and to subsequently purify the *5 esters by distillationunder reduced pressure, or by crystallization from alcohol (see United States Patent No. 1,800,862, Humphrey). Such pro cedure has not proved satisfactory in that the products are dark colored and hence undesirable for many'uses. ~ ' 'l Now, in accordance with this invention there is provided a method for the production of esters of terpene alcohols which is e?icientand eco nomical and which is productive directly of a terpene ester product which is non-crystalline and of 'a- light color, novel characteristics differ entiating it from the prior art and vwhich adapt for example, by re?uxing the pine oil, or pine oil out, with, for example, alcoholic potash, and the pine oil, or pine oil out may be, freed from anethol, after-the refluxing, by decanting, water Washing and fractionating at a temperature such ‘5 that the anethol’ and high boiling ethers will remain in the residue. In proceeding in accordance with this inven- 1 tion, pine oil containing terpene alcohols may be used, though it will be preferable to use a pine ‘10 oil out rich in terpene alcohols, say, for example, a pine oil out boiling within the range 200° C. to 220° 0., though the particular boiling range of the cut will not be material. The pine oil, or pine oil out, will be ?rst treated 15 for the removal of oxidation products and such it to wide use‘ in the commercial arts, for which similar esters were not heretofore adaptable. treatment may; for example, involve steam dis tilling the pine oil, or pine oil out, from caustic soda, by dry distilling from caustic, or by any other effective procedure. .20 ' In accordance with this invention, terpene al-, The pine oil, or pine oil out, after removal of 'cohols, pine oil‘containing terpene alcohols, or a oxidation products, will be esteri?ed with use pine oil out ‘rich in terpene alcohols, are sub of any suitable polybasic acid or anhydride, as, jected to treatment for the removal of oxidation for example, phthalic acid or anhydride, maleic products and the terpene alcohols then esteri?ed acid or anhydride, iumaric acid, sebacic acid, etc. :25 25 under conditions which will avoid oxidation, as The esteri?cation will be carried out in any by exclusion of air through carrying out the re usual manner, using, if desired, any suitable es action in an inert atmosphere. Inthe esteriiica teri?cation catalyst. However, essentially the tion the use of toluene, or an equivalent, to aid esteri?cation will be» carried out with avoidance in the removal of water of reaction will desirably of oxidation and such may be accomplished by 130 30 be used; On completion of the esteri?cation effecting the esteri?cation in an inert atmos the product will desirably be distilled from the phere, as, for example, in an atmosphere of reaction mass and the distillation will desirably hydrogen, nitrogen, carbon dioxide, or other inert be carried out with avoidance of oxidation, as by effecting the distillation in an inert atmosphere. gas. ‘Where it is desirable to remove ethers, such 35 35 The product will be non-crystalline and of a light as anethol and methyl chavicol, from the pine oil, color. . i or pine oil out, as has been indicated, such is 20 ' More‘ speci?cally, in accordance with this in vention‘ pine oil, or a pine oil out rich in terpene ‘alcohols, may be subjected to treatment for the removal of tertiary terpene alcohols before ester i?cation. The tertiary terpene alcohols may be removed from the pine oil, or pine o-il'cut, by effecting their dehydration, or splitting into ter pene hydrocarbons and water, prior to treatment 45 of the pine oil, or pine oil out, for the removal of oxidation products, by heating the pine oil, or pine oil'cut, with a dehydrating agent, such as fuller’s earth, iodine, sodium acid sulphate, etc. Again, if it is desirable to avoid the presence of 50 others, such as anethol and methyl chavicol, in the product, the pine oil, or pine oil out, may be subjected‘to treatment to isomerize the methyl chavicol to anethol and fractionated, leaving the anethol in the residue. The isomerization of 55 methyl chavicol to anethol may be accomplished, . readily accomplished, for example, by isomeriz ing the methyl chavicol, for example, by re?uxing the vpine oil, or pine oil out, with alcoholic potash, 40 decanting, water-washing and fractionating the pine oil, or cut,- from the high boiling ethers, be fore treatment for the removal of oxidation prod.‘ ucts. Where removal of the tertiary alcohols from 45 pine oil, or pine oil cut, is desired, such, as has been indicated, can be accomplished by effecting dehydration of the tertiary alcohols by, for ex ‘ample, heating the pine oil, or pine .oil out, with fuller’s earth, iodine, sodium acid sulphate‘, etc., -‘50 prior to treatment of the pine oil, or pine oil out, for removal of oxidation products. 7 In effecting dehydration of the tertiary alco holds in the pine oil, or pine oil out, a tempera ture within the range about 100° C‘. to about 55 2 2,136,000 200° C. may. be used and in eifecting the ester i?cation a temperature within the range about 125° C. to about 250° C. will be found satisfactory. Generally speaking, in carrying out the method in accordance with this invention, temperatures in of H+ (rosin, standard 7;” cube) and an acid number of 52. The product obtained by the above procedure may be distilled under reduced pressure to ob tain a 390% yield of ester which will have a color $1 excess of about 180° C. will be avoided in order grade WW+ (rosin, standard 7A," g.) and an to avoid c'arbonization, which will have a discol oring ‘effect upon the ultimate product. The 'acidnumber of 20. In the procedure described above the 3% ter esteri?cation will desirably be carried out with 10 distillation over of oils and water of reaction in ’ tiary alcohols obtained from the original pine oil order to avoid discoloration of the product and fcu't will be largely dehydrated during the esteri sult from such cause may be avoided by e?ecting The inert and unreacted materials such as h'y 15 drocarbons, excess pine oil alcohols, etc. on com dehydration of the tertiary alcohols. It will be understood that where in the claims appended hereto the term “pine oil” is used, it is intended that such term includes as equivalents pletion of the esteri?cation will desirably be dis tilled from the reaction mass in an inert at mosphere. . . pine oil as such and also pine oil cuts more or less It will be understood that the method in ac rich inosecondary terpene alcohols. 20 cordance with this invention, while more partic What I claim and desire to protect by Letters 20 ularly, adaptable for the treatment of terpene alcohols, and more especially of secondary ter Patent is: oil out rich in terpene alcohols, is adaptable for It in the reaction mass. Will be appreciated that the product, where the method is applied to the treatment of pine oil, 2. The method of producing a dicarboxylic acid ester of a terpene alcohol which includes ester ifying a terpene alcohol in an inert atmosphere. . .or a pine oil out, will comprise a mixture of ter .pene alcohol esters, since pine oil and pine oil . 30 cuts richin terpene alcohols will contain a plu an inert atmosphere. esteri?cation of terpene alcohols as present in pine oil, or in a pine oil cut, the tertiary alco~ hols will be dehydrated‘ rather than esteri?ed, when the tertiary terpene alcohols 'are not de will be present in the product. As more speci?cally illustrative of the practical ‘ester of a terpene alcohol which includes remov~ adaptation of the method invaccordance with this ' ing oxidation products from pine oil and reacting invention for the production of products in ac cordance therewith, for example, 11,000 parts of a the pin'eioil with av dicarboxylic acid to form an ‘while, avoiding oxidation of the pine oil. pine oil out boiling Within the range 195° C. to 4.5 ‘230° Grand, containing, for example, 54% sec ondary alcohols and 3% tertiary alcohols, is steam distilledv from caustic soda. To the dry distillate is then added 250 parts of phthalic anhydride and the reagents heated for about 80 hours at a tem perature of about 180°C. , the reaction mass being 55 7 - 4. The method of producing a dicarboxylic acid ester of a terpene alcohol which includes ester ifying a terpene alcohol in an inert atmosphere and distilling the resultant ester from, the reac tion mass in an inert atmosphere. 5. The method of producing a dicarboxylic acid hydrated by treatment of the pine oil, or a pine oilcut, prior to ‘esteri?cation, the esters thereof 40 3. The method of producing a dicarboxylic acid ester of a secondary terpene alcohol ‘which in 30 cludes esterifying a secondary terpene alcohol in rality of terpene alcohols, as, for example, borneol and fenchyl alcohol. Generally speaking, in the 35 v 1. The method vof producing a dicarboxylic acid ester 'of a terpene alcohol which includes ester ifying a terpene alcohol while avoiding oxidation pene alcohols as present in pine oil, or in a pine 25 the treatment of terpene alcohols as such. ester , of a terpene alcohol contained therein , 6. The method of producing a dicarboxylic acid ester of a terpene alcohol which includes remov ing oxidation products from pine oil and reacting the pine oil with a dicarboxylic acid to form an ‘ester of a terpene alcohol contained therein in an inert atmosphere. blanketed with carbon dioxide to prevent oxida tion. Desirably, toluene will be added in small quantities, from time to time to assist in the re '7. The method of producing a dicarboxylic acid .~ ,ester of a secondary terpene alcohol which in moval of water of reaction. pine oil and reacting the pine oil with a dicar The water of ‘re action will be distilled on togetherwith oils, which will distill off atthe temperature used. The oils will vdesirably not be returned to the reaction mass, since they will become partially oxidized and will e?ectdiscoloration of the product. In 60 proceeding, any suitable form of apparatus may be used and where the apparatus used is so de signed as to exclude the possibility of entry of air, the oils distilled oir may be returned to the reaction mass. ' ‘ ' , On completion of esteri?cation, the product will be vsteam distilled in an inert atmosphere,'as car bon dioxide, to remove hydrocarbons and excess .terpene alcohols, from the product, which re mains as a pale colored, amorphous residue. By 70 the procedure outlined aproduct amounting to 718 parts, or a yield of 97%, will be obtained. The product will be amorphous, will have a colorgrade 10 ?cation and will. cause some discoloration of the ultimate product. Such discoloration as may re— desirably an agent, as toluene, or the like, will be ‘used to aid in the removal of water of reaction. cludes dehydrating tertiary terpene alcohols in pine oil, removing oxidation products from the boxylic acid to form an ester of a secondary ter- . ; pene alcohol contained therein. 8. Thefmethod of producing a dicarboxylic acid ester of a terpene alcohol which includes dis— tilling pine oil from alkali to remove oxidation products therefrom and reacting the distilled pine oil with a dicarboxylic acid to form an ester of a terpene alcohol contained therein While avoid ing oxidation of the pine oil. , W 9. The method of producing a dicarboxylic acid ester of a terpene alcohol which includes steam / distilling pine oil from an'alkaline solutionv to re move-oxidation products therefrom and reacting a terpene alcohol in ‘the distilled pine oil with a dicarboxylic acid to form an ester of a terpene alcohol contained therein while avoiding oxida tion of the pine oil. JOSEPH N. BORGL'IN.