US2652406A - Method for the peeparation of - Google Patents
Method for the peeparation of Download PDFInfo
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- US2652406A US2652406A US2652406DA US2652406A US 2652406 A US2652406 A US 2652406A US 2652406D A US2652406D A US 2652406DA US 2652406 A US2652406 A US 2652406A
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- ester
- lactone
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- 238000000034 method Methods 0.000 title description 17
- 150000002596 lactones Chemical class 0.000 claims description 28
- 239000003054 catalyst Substances 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 238000007363 ring formation reaction Methods 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 description 27
- 238000006243 chemical reaction Methods 0.000 description 18
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 13
- 229910052753 mercury Inorganic materials 0.000 description 13
- 239000002253 acid Substances 0.000 description 10
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 125000004432 carbon atom Chemical group C* 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 238000000354 decomposition reaction Methods 0.000 description 6
- 150000005690 diesters Chemical class 0.000 description 6
- 229910052500 inorganic mineral Inorganic materials 0.000 description 6
- 239000011707 mineral Substances 0.000 description 6
- 238000007127 saponification reaction Methods 0.000 description 6
- 241000402754 Erythranthe moschata Species 0.000 description 5
- -1 Monocyclic lactones Chemical class 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 4
- 239000004327 boric acid Substances 0.000 description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 239000012230 colorless oil Substances 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical class OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 150000007524 organic acids Chemical class 0.000 description 3
- GQEZCXVZFLOKMC-UHFFFAOYSA-N 1-hexadecene Chemical compound CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- FKUPPRZPSYCDRS-UHFFFAOYSA-N Cyclopentadecanolide Chemical compound O=C1CCCCCCCCCCCCCCO1 FKUPPRZPSYCDRS-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 235000011149 sulphuric acid Nutrition 0.000 description 2
- LGQXXHMEBUOXRP-UHFFFAOYSA-N tributyl borate Chemical compound CCCCOB(OCCCC)OCCCC LGQXXHMEBUOXRP-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- NVIPUOMWGQAOIT-UHFFFAOYSA-N (E)-7-Hexadecen-16-olide Natural products O=C1CCCCCC=CCCCCCCCCO1 NVIPUOMWGQAOIT-UHFFFAOYSA-N 0.000 description 1
- LOKPJYNMYCVCRM-UHFFFAOYSA-N 16-Hexadecanolide Chemical compound O=C1CCCCCCCCCCCCCCCO1 LOKPJYNMYCVCRM-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- NVIPUOMWGQAOIT-DUXPYHPUSA-N 7-hexadecen-1,16-olide Chemical compound O=C1CCCCC\C=C\CCCCCCCCO1 NVIPUOMWGQAOIT-DUXPYHPUSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 235000006679 Mentha X verticillata Nutrition 0.000 description 1
- 235000002899 Mentha suaveolens Nutrition 0.000 description 1
- 235000001636 Mentha x rotundifolia Nutrition 0.000 description 1
- 241001670273 Ooia Species 0.000 description 1
- 241000209504 Poaceae Species 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 125000005619 boric acid group Chemical group 0.000 description 1
- MMBBKYKVRZDICO-UHFFFAOYSA-N butyl 16-hydroxyhexadecanoate Chemical compound CCCCOC(=O)CCCCCCCCCCCCCCCO MMBBKYKVRZDICO-UHFFFAOYSA-N 0.000 description 1
- 125000005586 carbonic acid group Chemical group 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000007799 cork Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 150000003997 cyclic ketones Chemical class 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- VBKONVSYRQSMHY-UHFFFAOYSA-N methyl 14-hydroxytetradecanoate Chemical compound COC(=O)CCCCCCCCCCCCCO VBKONVSYRQSMHY-UHFFFAOYSA-N 0.000 description 1
- UMGJSBQEGITOSK-UHFFFAOYSA-N methyl 16-acetyloxyhexadec-7-enoate Chemical compound COC(CCCCCC=CCCCCCCCCOC(C)=O)=O UMGJSBQEGITOSK-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 238000006798 ring closing metathesis reaction Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/26—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D307/30—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/32—Oxygen atoms
- C07D307/33—Oxygen atoms in position 2, the oxygen atom being in its keto or unsubstituted enol form
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D313/00—Heterocyclic compounds containing rings of more than six members having one oxygen atom as the only ring hetero atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D315/00—Heterocyclic compounds containing rings having one oxygen atom as the only ring hetero atom according to more than one of groups C07D303/00 - C07D313/00
Definitions
- Kerschbaum consists in heating under particular conditions the silver salts of halogenated fatty acids in which the halogen atom is in at least the 12th position in relation to the carboxyl group.
- three lactones having an odor of musk were prepared, the 1,15-pentadecanolide, the 1,16-hexadecanolide and the 1,16 hexadecene- 7-o1ide (ambrottolide), but the yields obtained were not reported.
- the process of the present invention is a process for the preparation of these lactones which is simple and rapid in operation; which uses standard apparatus and common reagents; and finally which gives these lactones with very great purity and a high yield.
- an ester of composition R OOO-R can be prepared by the interaction of two esters R. COOR, and R COO--R in the presence of a catalyst of the exchange of radicals; R -COO and Rfi-COO being the anions of carboxylic acids; R and R being alkyl radicals; the equilibrium equation is the following in which R is a chain containing at least 11 carbon atoms.
- This radical R can be split into two parts R or R each representing an open chain containing at least 5 carbon atoms; the above ester can then be formulated as In this form it presents a striking analogy with an equimolecular mixture of the esters Experience has shown that in certain conditions which will be specified later, this body (i. e. the diester) behaves exactly like such a mixture in forming the lactone V
- this body i. e. the diester
- Rfi-I-Rfi which, replacing once more R for Rfi-I-Rfi, can be "If R and R are radicals containing few carbon atoms, the ester R -COO-R is very volatile, it escapes from the reaction zone, the equilibriurn is disturbed and the Reaction II proceeds from left to right yielding the desired lactone.
- a diester itself obtained by the combination of I an omega-hydroxwester of the form U V V Ho.r:..(:ooia either with an organic acid R COOl-ior with a mineral acid AOI-I, the radical .R comprising at least 11 carbon atoms.
- This decomposition takes 7 place under the actionof heat with if necessary a reduction of pressure and in'the presence of a standard catalyst of the exchange of radicals.
- one of the important features of the present invention lies in the choice of the organic acid R COi-i (or oi the mineral acid AOH) and of the alcohol RF-OH so that by virtue of the high volatility of the ester lEt -COOR (or AOR the Reaction Ill can take place immediately and at a temperature low enough to enable-an excellent yield of monomeric lactone to be obtained. Thanks to the mildness of the reagents used and the conditionsv of preparation, the lactones obtained by this process are chemically-and oliactorily very pure. 7 V i No reaction of this type has been mentioned in 7 the-literature and this-new reaction is fundamental to the present invention.
- the second oody formed which is here an ester-must be very volatile and distil over at a temperature substantially lower than does the lactone; in practice as will be seen from the examples given later, the ester formed at the same time as the lactone is gaseous under the conditions of the reaction and its' elimination is therefore instantaneous.
- radical R can be a straight or branched'chaing' it may be homogeneous, that is to say comprise only saturated radicals consisting only of carbon and hydrogen or it may be heterogeneous that is to say comprise one or more double or triple bonds, one or more hetero-atoms (such as oxygen, nitrogen, sulphur, etc.) whatever may be the internal linkingof these different radicals or groups;
- Iheradical R of the acid"R COOI-l which esterifies the Oil of the hydroxyester can be hy-' drogen or a simple radical containing a low number of carbon atoms; thus the acid R -CQOH will be for example formic acid, acetic. acid, or one of their immediate homolcgues chosen so as to obtain after the reaction a very'volatile ester Similarly the mineral radical AO corre-.
- alsO abieto esterify the OHof the hydroxy-estr will be chosen among the mineral acid radicals giving .with the alcohol Bi 0H a very volatile ester AORF; by way of an indicative and not limitatiye examplaboric, carbonictand sulphuric acids may be mentioned.
- the alcohol R -OH which esterifies the acidity of the omega-hydroxy acid HORLOOI-I will preferably be chosen among the lower alcohols, that is to say amongmethyl, ethyl, propyl,
- the temperature and pressure will bechosen at the discretion of the operator according to the nature of the constituents of the reaction and their volatility.
- Example 3 23.2 gms. of methyl-14-hydroxy-tetradecanoate were converted into boric ester by treatment with butyl borate. The butanol formed was driven .off, :thenzthe. excessof Jouty-lborate gsodium bytylate was introduced and heating was effected under a reduced pressure of 3 mm. of mercury. With the heating bath at 230-240 C., 12.5 gins. of distillate were collected during one hour.
- the distillate was a colorless oil having an odor of musk, with the following characteristics:
- Example 4 20 grams of methyl-.Z-hydroxy-dodecanoate were converted into boric ester bytreatment with boric acid.
- the diester was heated to 220-230 C. under a reduced pressure of 3 mm. of mercury, in the presence of sodium'methylate. In 80 minutes 10.1 mm. of distillate were collected.
- Example 5 23.7 gms. of methyl-,l-acetyloxy-IS-oxa-15- tetradecacarbanoate heatedto 220-230" C. under a reduced pressure of 3 of mercury, in the presence of sodium methylate, yielded 13.05 .gms. of distillate in a period of 70 minutes.
- This distillate was a colorless oil, having an odor of musk, distilling completely between and 112 C. at a pressure of 2.5 mm. of mercury. It "had the following constants:
- the resulting diester was heated at 220-230 C. under a reduced pressure of 3 mm. of mercury, in the presence'of sodium methylate. 18.45 gms. of pure lactone were obtained, a yield of 72 per cent of the theoretical. It was a colorless liquid with 1 an odor of amber and musk, which had the following constants:
- CieHsaOz (with a double bond between two atoms of carbon, one oxygen atom being linked with a carbon atom'through a double bond and the other atom of oxygen being'linked with a carbon atom through a single bond) 75.07 Saponification value; 224.0 Calculated for Ciel-12802 222.2 Iodine value (theory 100.7) 98.5
- a method for producing substantially pure monocyclic lactones including at least 12 carbon atoms in the lactone ring comprising providing at raised temperature and under reduced pressure, in the presence of a catalyst, the cyclization of a diester A-O(CH2) n-CO OR2 wherein n is an integer from 10 to .15 inclusive, R2 an alkyl radical selected from the group including methyl, ethyl, propyl and butyl, and A the radical of an acid adapted to produce an ester of high'volatility with the said alkyl radical, said reaction producing a lactone (CH2)n CO and an ester A-.O-Ri2 much more voltatile than the lactone, allowing said ester to evolve immediately in gaseous form and recovering the pure liquid lactone.
- n is an integer from 10 to 15 inclusive
- R2 an alkyl radical selected fromthe group in cluding methyl, ethyl, ,propyl and butyl'and A the radical of an acid selected from the group consisting of boric, carbonic and sulfuric acids,
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Patented Sept. 15, 1953 METHOD FOR THE PREPARATION OF LACTONES 4 Laurent Lucien Crabalon a, Grasse, France, as-
signor to Societe Anonyme des Etablissements Roure-Bertrand Fils & Justin Dupont, Paris, France, a corporation of the French Republic No Drawing. Application August 13, 1948, Serial No. 44,227. In France September 20, 1947 3 Claims.
Monocyclic lactones having more than 12 chain members in the lactone ring were studied at length by Kerschbaum (German Patent No. 449,217 of the 6th of March 1926 and Ber. Deutsch. Chem. Ges. 1927, vol. 60, pp. 902 ff.) who showed that they could not be obtained by the ordinary methods of esterification because such methods gave rise to polymers without interest.
The special procedure described by Kerschbaum consists in heating under particular conditions the silver salts of halogenated fatty acids in which the halogen atom is in at least the 12th position in relation to the carboxyl group. In this way three lactones having an odor of musk were prepared, the 1,15-pentadecanolide, the 1,16-hexadecanolide and the 1,16 hexadecene- 7-o1ide (ambrottolide), but the yields obtained were not reported.
Since that time other methods have been worked out for the preparation of these lactones, particularly the following:
a. The oxidation of cyclic ketones (Ruzicka and Stoll Helv. Chim. Acta 1928, 11, 1159; cf. also French Patent No. 657,971 of the 23rd of July 1928).
b.The internal ring-closure of oxyacids in a highly diluted medium (French Patent No. 773,651 of the 3rd of September 1934 and Certificate of Addition No, 46,623 of the 19th of May 1934).
c. The depolymerization of the corresponding polyesters (French Patents No. 768,807 of the 28th of May 1934 and No. 796,410 of the 22nd of January 1936) d. The treatment of certain halogenated fatty acids in an alkaline medium and in the presence of certain low boiling point solvents (French Patent No. 839,188 of the 11th of June 1933 of Hunsdiacher, Erlbach and Vogt).
e. The heating of an ester of an oxyacid in the presence of a catalyst of the exchange of functional groups (French Patent No. 830,689 of the 13th of December 1937 and Certificate of Addition No. 49,302 of the th of March 1938) etc.
The practical operation of these methods presents various inconveniences such as extreme dilution, the use of high vacua, the need for using special apparatus, the use of uncommon reagents, extreme slowness of the reactions, decomposition of the products, etc. It should be added that the yields also are not always satisfactory and that the quality of the lactones obtained leaves something to be desired, which is a particularly serious shortcoming in products intended for perfumery,
The process of the present invention is a process for the preparation of these lactones which is simple and rapid in operation; which uses standard apparatus and common reagents; and finally which gives these lactones with very great purity and a high yield.
This process is based on a reaction of internal double decomposition of certain esters in the presence of catalysts favoring the exchange of functional groups. A double decomposition reaction of this kind for the preparation of oranic esters was proposed in United States of America Patent No. 1,860,092 of the 31st of October 1929 George Graves assignor to E. I. du Pont de Nemours and Co.
In this patent it is stated that an ester of composition R OOO-R can be prepared by the interaction of two esters R. COOR, and R COO--R in the presence of a catalyst of the exchange of radicals; R -COO and Rfi-COO being the anions of carboxylic acids; R and R being alkyl radicals; the equilibrium equation is the following in which R is a chain containing at least 11 carbon atoms. This radical R can be split into two parts R or R each representing an open chain containing at least 5 carbon atoms; the above ester can then be formulated as In this form it presents a striking analogy with an equimolecular mixture of the esters Experience has shown that in certain conditions which will be specified later, this body (i. e. the diester) behaves exactly like such a mixture in forming the lactone V The present invention, the
which, replacing once more R for Rfi-I-Rfi, can be "If R and R are radicals containing few carbon atoms, the ester R -COO-R is very volatile, it escapes from the reaction zone, the equilibriurn is disturbed and the Reaction II proceeds from left to right yielding the desired lactone.
Experience has also shown that the Reaction II can proceed in the same way if the carboxylic anion R -COO-' is replaced by a mineral anion AQ- able to form a very volatile ester with the alcohol R. Ol-I; in that case the equation becomes 7 or, what comes to the same thing mechanism of which has just been explained, is thus essentially characterised by the decomposition, which can be regarded as an internal exchange of radicals, of
a diester itself obtained by the combination of I an omega-hydroxwester of the form U V V Ho.r:..(:ooia either with an organic acid R COOl-ior with a mineral acid AOI-I, the radical .R comprising at least 11 carbon atoms. This decomposition takes 7 place under the actionof heat with if necessary a reduction of pressure and in'the presence of a standard catalyst of the exchange of radicals.
As can be seen from the above, one of the important features of the present invention lies in the choice of the organic acid R COi-i (or oi the mineral acid AOH) and of the alcohol RF-OH so that by virtue of the high volatility of the ester lEt -COOR (or AOR the Reaction Ill can take place immediately and at a temperature low enough to enable-an excellent yield of monomeric lactone to be obtained. Thanks to the mildness of the reagents used and the conditionsv of preparation, the lactones obtained by this process are chemically-and oliactorily very pure. 7 V i No reaction of this type has been mentioned in 7 the-literature and this-new reaction is fundamental to the present invention. The only known reaction which could in certain directions 'be regarded as approaching that which'has just been described is the decomposition mentioned above'of'an ester of anoxyacid'HO.R.CO0-R with formation of a la'ctone Y :aooo
and an alcohol ROH (French Patent No.
830,689) but to make clear the essential difierences between the two processes, it suiiices to point out that: r
, a: The French Patent No 830.689 is concerned- -with an exchange reaction between an alcohol and an ester and not between two esters, or, what ,comes to the same thing, in the patent there'is formation of an alcohol as the second'product while in the process herein claimed there is formation of an ester as the second product.
and has a boiling point above 100 C. at a pressure of 2 mm. of mercury.
In the new process here described, exactly the opposite applies; the second oody formedwhich is here an ester-must be very volatile and distil over at a temperature substantially lower than does the lactone; in practice as will be seen from the examples given later, the ester formed at the same time as the lactone is gaseous under the conditions of the reaction and its' elimination is therefore instantaneous. V
c. In the French Patent No. 330,689 in order that the exchange reaction may take place it is essential to carry theheterogeneOus mixture'to a high'temperature and to eliminate'thelactone from thereaction zone when and as it is formed, utilising the well-known property of'polyols of carrying ofi less volatile bodies with theirvap-crs; this is the phenomenon of glycolic co-distillation which has been the subject of many investigations (of particularly Sabetay Ann. Chimie Analytique 1939, vol. 21, p. 173, and 1940, vol. 22, p. 217). 1
In the process here claimed there is nothing comparable; there is nopossibility of the lactone being'carried off by the ester formed and, the equilibrium being rapidly disturbed by the volatilization of the ester, the formation of the lactone' takes place very easily at arnuch lower temperature. It suflices thereafter to raise the 7 temperature slightly to distil 01f the l-actone unthought of as split into two sections B a-R comprises at least 11 carbon atoms in open chain and may reach a substantially higher figure; this,
radical R can be a straight or branched'chaing' it may be homogeneous, that is to say comprise only saturated radicals consisting only of carbon and hydrogen or it may be heterogeneous that is to say comprise one or more double or triple bonds, one or more hetero-atoms (such as oxygen, nitrogen, sulphur, etc.) whatever may be the internal linkingof these different radicals or groups;
Iheradical R of the acid"R COOI-l which esterifies the Oil of the hydroxyester can be hy-' drogen or a simple radical containing a low number of carbon atoms; thus the acid R -CQOH will be for example formic acid, acetic. acid, or one of their immediate homolcgues chosen so as to obtain after the reaction a very'volatile ester Similarly the mineral radical AO corre-.
sponding to the mineral acidAOI-l, alsO abieto esterify the OHof the hydroxy-estr will be chosen among the mineral acid radicals giving .with the alcohol Bi 0H a very volatile ester AORF; by way of an indicative and not limitatiye examplaboric, carbonictand sulphuric acids may be mentioned.
- Finally. the alcohol R -OH which esterifies the acidity of the omega-hydroxy acid HORLOOI-I will preferably be chosen among the lower alcohols, that is to say amongmethyl, ethyl, propyl,
butyl, etc. alcohols,;always with'a view to obtain- ,7 K
ing, along with the desired lactone, as volatile as here claimed, a body known for its properties .of
catalyzing theexchange of radicals will be used; without the list being intended to be limitative, the two following groups are particularly recommended: the alkaline or earth alkaline derivatives of moncor polyvalent alcohols orphenols; and more or less ionized bodies with an acid reaction, such as sulphuric or phosphoric acid, organic acids, arylsulphonic acids, etc.; it will be understood that the proportion of catalyst cannot be laid down in advance and will be determined in each case according to the activity of the catalyst and the speedof reaction it is desired to obtain; in a more general way, the present invention is not tied to the use of a particular catalyst.
The temperature and pressure will bechosen at the discretion of the operator according to the nature of the constituents of the reaction and their volatility.
The examples which follow will enable the possibilities of practising the invention to be appreciated; it will be understood that the examples are only given by way of indication; they in no way limit the invention which has been described above.
Example 1 Within the limits of experimental error, these constants are those of pure 1-16-hexadecanolide, given in the literature (Helv. C'him. Acta, vol. 11, 1171 (1928).
Example 2 25.7 grams of butyl-16-hydroxyhexadecanoate were converted into boric ester by means of 1.56 m. of boric acid. The water formed was driven off, the diester heated under a reduced pressure of 3 mm. of mercury in the presence of sodium methylate. With the heating bath at 180-190 Cta very mobile colorless liquid distilled off. This was collectedjit weighed 5.05 gm. This was butyl borate, for it distilled completelyat 122-124 C. under a pressure of 24 mm. of mercury, and at 97-99 C. under a pressure of 6 mm. of mercury; index of refraction n =1.4120 water hydrolyzed it into butanol and boric acid.
Heating under a vacuum was continued and when the temperature of the heating bath reached 230-240 C., 13.1 grams of distillate were collected in 2 hours, the constants of which were practically identical with those of the lactone ob tained in Example 1.
' Yield 64.8 per cent of theoretical.
Example 3 23.2 gms. of methyl-14-hydroxy-tetradecanoate were converted into boric ester by treatment with butyl borate. The butanol formed was driven .off, :thenzthe. excessof Jouty-lborate gsodium bytylate was introduced and heating was effected under a reduced pressure of 3 mm. of mercury. With the heating bath at 230-240 C., 12.5 gins. of distillate were collected during one hour.
The distillate was a colorless oil having an odor of musk, with the following characteristics:
Distilled completely between 110 and 112. .C. at
solidification point, 27 C.
Index of refraction 11. 1.4701
Density 014 0.9530
'Saponification value, 246.7
Within the limits of experimentalerror, these constants are those of 1-14-tetradecanolide.given in the literatur (Helv. Chim. Acta, vol. 11, 1171 (1928) )j.
Yield 61 per cent of the theoretical.
Example 4 20 grams of methyl-.Z-hydroxy-dodecanoate were converted into boric ester bytreatment with boric acid.
The diester was heated to 220-230 C. under a reduced pressure of 3 mm. of mercury, in the presence of sodium'methylate. In 80 minutes 10.1 mm. of distillate were collected.
This was a colorless oil, sprinkled with small shining white crystals. Its odor-was disagreeable; it recalled that of a burnt-out candle and of a mouldy cork bung, with a slight musty smell of mint.
Under fractional distillation, at2 mm. of mercury, these 10.1 gms., yielded between 83 and 85 C., 8.5 gms. of acolorless oil having the same odor, and 1.45 gm. of residue.
The distilled oil had the following characteristics:
Density r14 0.9800 Refractive index n 1.4715 Saponification value 280.7
Within the limits of experimental error these constants are those of 1-12-dodecanolide given in the literature (Helv. Chim. Acta, vol. 13, 1120 (1935-) Stoll and Rouve).
The yield was 49.3 per cent of the theoretical while Stoll and Rouv obtained only 16 per cent by the method of great :dilution.
The residue from the fractionation, twice recrystallized from alcohol, melted at 104 C. and had a saponi-fication value of 282.8. This is the theoretical "value for the dilactone for which Stoll and Rouv give a melting point of 101.
Example 5 23.7 gms. of methyl-,l-acetyloxy-IS-oxa-15- tetradecacarbanoate heatedto 220-230" C. under a reduced pressure of 3 of mercury, in the presence of sodium methylate, yielded 13.05 .gms. of distillate in a period of 70 minutes. This distillate was a colorless oil, having an odor of musk, distilling completely between and 112 C. at a pressure of 2.5 mm. of mercury. It "had the following constants:
solidification point C Density d4" 0.9950 Refractive index 12 1.4702 Molecular refraction R found 67.86 Calculated for C'14H26 O O O" 67.95 Saponification value 235.2
Calculated forCmHzeos V 68 percent of the theoretical.
Y i Example 6 V 28.8 g'ms. of methyl-1-hydroxy-4-oxa-16-pentadecacarbanoate were treated with boric acid.
The resulting diesterwas heated at 220-230 C. under a reduced pressure of 3 mm. of mercury, in the presence'of sodium methylate. 18.45 gms. of pure lactone were obtained, a yield of 72 per cent of the theoretical. It was a colorless liquid with 1 an odor of amber and musk, which had the following constants:
Boiling pointat 2 mm. of mercury C 113-115 Refractive index n 1.4683 Density d4 0.9853 Molecular refraction R found 72.25 Calculated for Ciel-I28 O' O' C)"w 72.45 Saponification value found 221.2 Calculated for cyclo -l-l-dioxa-pentadca-Z-carbanone i (CHEM-140E;
218.75 V (ensu -co Example 7 13-.80 gms. of methyl-16-acetyloxy-7-hexadecenoate were heated at 220250 under a reduced j, pressure of 3 mm. of mercury, in the presence of sodium methylate. 'In 1%. hours, 8.37 gms.
, ofdistillate were collected in the form or" a colorless oil having a strong'odor of musk.
' This distillate had the following characteris tics: g g H Redistilled at 3 mm. of mercury, it distilled over completelybetween -l iz and 144 C.
Density (14 Refractive index n 1.4816 Molecular refraction 'R found 74.98
Calculated for CieHsaOz (with a double bond between two atoms of carbon, one oxygen atom being linked with a carbon atom'through a double bond and the other atom of oxygen being'linked with a carbon atom through a single bond) 75.07 Saponification value; 224.0 Calculated for Ciel-12802 222.2 Iodine value (theory 100.7) 98.5
Within the limitsof experimental error, these constants are those of l'hexadecene 1.16'olide (ambrettolide) given. in 'the literature (Helv.
; Chim. Acta, V01. 17, 1612(1934) The yield of the operation in monolactone was "78.4 per centofthe theoretical; 1
As has already been mentioned, these exam-1, ples' are described'only by way of indication and not as limiting the invention; in particular the substances mentioned could, each in its category,
bereplaced by others having analogous proper-- tiesysimilarly the numerical particulars given 7 couldbe varied within wide limits without departing from the scope of the invention. V
What I claim is:
1; A method for producing substantially pure monocyclic lactones including at least 12 carbon atoms in the lactone ring, comprising providing at raised temperature and under reduced pressure, in the presence of a catalyst, the cyclization of a diester A-O(CH2) n-CO OR2 wherein n is an integer from 10 to .15 inclusive, R2 an alkyl radical selected from the group including methyl, ethyl, propyl and butyl, and A the radical of an acid adapted to produce an ester of high'volatility with the said alkyl radical, said reaction producing a lactone (CH2)n CO and an ester A-.O-Ri2 much more voltatile than the lactone, allowing said ester to evolve immediately in gaseous form and recovering the pure liquid lactone.
2. A method for, producing substantially pure wherein m is an integer from o to 3 inclusive and '11 is an integer from 10 to 15 inclusive, R2 an alkyl radical selected from the group including methyl, ethyl, propyl and butyl, said reac- 1 tion producing a lactone evolve immediately in gaseous form and recover{ ing the pure liquid lactone.
3. A method for producing substantially pure monocyclic lactones including at least 12 carbon.
atoms in the. lactone ring, consisting in providing at raised temperature and under reduced pressure, in the presence of a catalyst, the cyclization of a diester A-O(CI-I2) n.-COOR2, wherein n is an integer from 10 to 15 inclusive, R2 an alkyl radical selected fromthe group in cluding methyl, ethyl, ,propyl and butyl'and A the radical of an acid selected from the group consisting of boric, carbonic and sulfuric acids,
said reaction producing a lactone ems-co and an ester AO-Rz much more volatile than the lactone, allowing'said' ester toevolvejimmediately in gaseous form and recovering the pure liquidlactone. 7
LAURENT LUCIEQN' C ABALQNA.
References Cited-in'thefile oi this patent UNITED STATES PATENTS Number Name 1 Date M 1 7 2,234,551 Collaud -1- Mar. 11, 19 :1 2,301,827 Stoll- Nov. 10, 1942 2,417,151 I conaud Mar; 11,1947
Claims (1)
1. A METHOD FOR PRODUCING SUBSTANTIALLY PURE MONOCYCLIC LACTONES INCLUDING AT LEAST 12 CARBON ATOMS IN WHICH LACTONE RING, COMPRISING PROVIDING AT RAISED TEMPERATURE AND UNDER REDUCED PRESSURE, IN THE PRESENCE OF A CATALYST, THE CYCLIZATION OF A DIESTER
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2652406A true US2652406A (en) | 1953-09-15 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3189619A (en) * | 1962-09-25 | 1965-06-15 | Exxon Research Engineering Co | Synthesis of carpolactone |
| US4490404A (en) * | 1983-07-18 | 1984-12-25 | International Flavors & Fragrances Inc. | Flavoring with macrocyclic lactone |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2234551A (en) * | 1941-03-11 | Preparation of lactones | ||
| US2301827A (en) * | 1942-11-10 | Process of making higher aliphatic | ||
| US2417151A (en) * | 1947-03-11 | Composition of matter with a scent |
-
0
- US US2652406D patent/US2652406A/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2234551A (en) * | 1941-03-11 | Preparation of lactones | ||
| US2301827A (en) * | 1942-11-10 | Process of making higher aliphatic | ||
| US2417151A (en) * | 1947-03-11 | Composition of matter with a scent |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3189619A (en) * | 1962-09-25 | 1965-06-15 | Exxon Research Engineering Co | Synthesis of carpolactone |
| US4490404A (en) * | 1983-07-18 | 1984-12-25 | International Flavors & Fragrances Inc. | Flavoring with macrocyclic lactone |
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