US1799536A - Twvpom - Google Patents

Description

cation H. 105,677, Class 12 o,

Patented Apr. 7, .1931

UNITED! STATES PATENT LEoPoLn RUzIcKA, OF DE BILT,

' ANONYME M. NAEF & co., or

LAND

NEAR'UTREGHZIQ, NETHERLANDS, ass anon 'ro SOCIETE GENEVM-SWITZERLAND, A CORPORATION or swrrznn- PROCESS r03 THEPBEPAR-ATION or THE. MONOGYCLIC' nacronns HAVING FOURTEEN i T0. EIGHTEENYRIIIG MEMBERS no Drawing, Application filed. July 16,1928,

Closed; chain lactones: having, more than seven ring members have. not hitherto been obtainable in the pure state: M. Kerschbaum has however stated in the Berichte der deut- 4 5 schen Chemischen Gesellschaft, 1927, volume 60, pages 902 and tollowing,that in native substances a lactone is present having;16' and 17 'ringmembers. It is also stated in the'speciiication of German patent appl published the 25th-May 1927, that synthetic lactones are produced having 16 and 17 ring members, -which are formed by heating with silver oXid of brominated'fatty acids in which the atom of bromine and the carboXyl group are at the opposite, ends of the chain. 'All these lactones-are described as beingliquids whlch do: not possess clearly defined boiling points the yields of these products ln' the syntheti- 20'c'al process are sosmall, that a preparation of the products in the pure state has apparently that now not been possible.-

I have however found that it is possible to obtain such lactones-in the chemically pure stateandin a considerable. yield byheating carbocyclic ketones having a large/number of ring members suchas those descrlbed in the United States Patent 1,673,093 and the United States patent applications Serial No.

.149534- to No, 149,544 now Patents Nos.

1,702,842 to 1,702,852 respectively, issued February 19, 1929, with monopersulphuric acid ata temperature of about 30 to I60 degrees-centigrade.

' 5 l I thus did obtain from cyclotridecan'one the Y 12.-oXy-dodecane-l-carboxylic lactone oi acidjfrom cyclotetradecanone thelactone' of 13-oxy-tridecane 1-carboxylic acid; from ,cyclo-pentadecanone (exaltone) the lactone of 14-oXy-tetradecane-l-carboxylic acid (exaltolid) from cyclo-hexadecanone the lactone of 15-0Xy-pentadecane-l-carboxylic acid and iroin cyclo-heptadecanone (dihydrozibetone) the lactone of 16-oXy-heXadecan-1- 5 carboxylic acid. Allthese lactones are solid at a temperature above 25 degrees centigrade and possess clearly defined boiling ,points, 1

In a similar manner the corresponding lactones can be obtained from alkylated ketones 1 described in: the

U. .S'. Patents 1,673,093,

page. 862.

Serial No. 293,310, and in switzerland'luly 27, 1927.

1,7 02,842 to 1,702,852 inclusively; for instance. from 2-methyl-cyclopenta-decane-lone (lqnethyhexaltone) a mixture of lactones of the 14-oXy-14-methyl-tetradecane-1 carboxylic acid and the 14-oxy-1-methyl-tetradecane-l-carboxylic acid and from 3- methyl cyclopentadecan-e-1-one (muscone) a mixture of lactones of the 14-oXy-13-methyltetrade'cane-1-carboxylic acidand 14-oxy-2- methyl-tetradecane-l-carboxylic acid.

It was however already known to be possible to obtain. lactones having'respectively7 or 8 rmgmembers by treating ketones having 6 or Tringmembers with monopersulphuric' acid, as per Baeyer & Villiger, Berichte der deutschen Chemis-chen Gesellschaft, 1899, volume 32, page 3625 and 1900, volume 33, There appeared however that only such ketones give a good yield of lactones, which possess beside the ketone group substituents such as the isopropyl group and themethyl group. However, ketones which ,besides the keto-group do not possess any substituent did give either no lactone at all oronly a small amount thereof. But then one has to work below 20 degrees centigrade,

as at a higher temperatureonly the splitting product of the lactone, the oXy-acid, is formed. It could therefore not be expected thatketones having a larger number of ring members might give at a higher temperature a yield of more than 50 per cent of pure lactone, even if theypossess lateral chains approaching the keto-group. The stability of 'these' lactones against: warm monopersulphuric acid is so much more remarkable as a smallstability of the'same against hydrolizing agents would rather be expected from the known facility to. form lactones 1 having more than "sevenjring members.

When onthe contrary, the inonopersulphuric acid is allowed to act upon the higher membered ketones under the conditions indicated by v. Baeyer&'Villiger, there is obtained onlyia small quantity of the lactone, and in v its place the peroxide ofthe ketone is formed.

When my working conditions are ,maintained the production of these peroxides is avoided.

The constitution of the prepared unmethylated lactones was proved by splitting the same by means of boiling potash lye to the corresponding oxyacids which when oxidized'with chromic acid are'transformed into dicarboxylic acids having the same number of carbon atoms.

f The herein described lactones have an odorresembling that of musln civet or that of amber and may be employed in place of such perfumes or as raw materials for the preparation of similar products.

The preparation of lactones having 14 to 18 ring members represents in itself an important technical progress, as it is very important for the use of a substance as a perfume to remove from the same any impurities which may influence the odor thereof.

Example 1 27 grams cyclo-pentadecanone (exaltone) are dissolved in gr. petroleum benzine and added with a filtered solution of 160 gr. persulphate of potassium in 400 gr. concentrated sulphuric acid and 74: gr. water, this addition being made so rapidly that the temperature of the mixture remains about degrees centigrade. A too great riseof temperature may be avoided by an exterior cooling with ice. After standing'during several hours the mixture is poured on ice and the layer oi benzine is separated. By shaking the mixture with a solution of soda, acid products are extracted. By treating the neutral portion with a 0 solution of semicarbazide the remaining small quantities of unchanged cyclo-pentadecanone which are contained therein are transformed into the semicarbazone. The easily soluble lactone of the l l-oxy-tetradecane-l-carboxylic acid may then be extracted by means of petroleum spirit This lactone boils at 176 degrees centigrade under 15 mm. pressure, solidifies quickly into needles melting at 31 to 32 degrees centigrade and presents the following characteristics:

D *=0.944l7, n lailof).

D means the density measured at a temperature of 83 degrees Centigrade and relates to water of 4 degrees centigrade;

02 or N means refractive index of the D-line of the spectrum determined at a temperature of 33' degrees centigrade.

Example 2 grees centigrade and presents the following characteristics =O.959O n,', =1.4649.

Example 3 Cyclo-tetradecanone is treated in the manner described in Example 1. ,After the treatment of the neutral product of reaction with a solution of semicarbazide the lactone of l3-oxy-tridecane-l-carboxylic acid is extracted by means of petroleum spirit. It boils at 165 degrees Centigrade under 15 mm. pressure, melts at 29 to 30 degrees centigrade and presents the following characteristics:

D =0.9528; "n =1/l662. Example 4 Cyclo-hexadecanone is treated in the manner described in Example 1. After the treatment of the neutral product of reaction witha solution of semicarbazid the lactone of 15-oxy-pentadecane-l-carboxylic acid is extracted by means of petroleum spirit. It boils at 188 degrees centigrade under 15 mm. pressure, melts at 35 to 36 degrees centigrade and presents the following characteristics:

Example 5 Cyclo-heptadecanone (dihydro-zibetone) is treated in the manner described in EX- ample 1. After the treatment ofthe neutral reaction product with a solution of semicarbazide the lactone of 16-oXy-hexadecane-1- carboxylic acid is extracted by means of petroleum spirit; it boils at 19% degrees centigrade under 15 mm. pressure, melts at 11 to 42 degrees centigrade and presents the following characteristics Dfi =O.9326; 111, 1.4669. Example 6 D =0.93O1; n =1.4611.

Example 7 3 methyl-cyclopentadecane-1-on (muscone) is treated in the manner described in Example 1. After the treatment of the neutral reaction product with a solution of semicarbazide the mixture of the lactencs of the 14-oXy-13-methyl-tetradecane-l-carboxylic acid and 14-oxy-2 methyl-tetradecane-l-carboxylic acid is extracted by means of petroleum spirit. The mixture of lactones boils at 180 degrees centigrade at 15 mm. pressure and presents the following characteristics v WVith respect to the number of ring members mentioned in the claims 1 and 2 the following explanation is given:

By 14 to 18 ring members applicant means that besides the 13 to 17 carbon atoms there is furthermore one oxygen atom which by the conversion of the ketones into the lactones is inserted as ring member. That means in a general manner: 4

The lactone obtained from a ketone possesses one ring member more than the ketone, this ring member being an oxygen atom according to the following formula:

1. A process for the preparation of the monocyclic lactones having 14 to 18 ring members, consisting in heating monocyolic ketones having 13 to 17 ring members with persulphuric acid. 7 i

2. A process for the preparation of the monocyclic lactones having 14 to 18 ring members, consisting in heating monocyclic ketones having 13 to 17 ring members with persulphuri'c acid at a temperature of about 30 to 60 degrees Centigrade.

3. A process for thepreparation of the lactone from 14-oxy-tetradecane-l-carboxylic acid, consisting in heating cyclo-pentadecanone with persulphuric acid.

4. A process for the preparationof the lactone from 14-oxy-tetradecane-1-carboxylic acid, consisting in dissolving. cyclo-pentadecanone in petroleum benzine. adding a solution of persulphate of. potassium' in sul phuric acid and water, maintaining the temperature atabout 50 degrees centigrade, after several hours standing, pouring the mixture on ice, separatingthe layer of ben zine eX- tracting the acid products by means of a solution of soda, treating the neutral reaction product with a solution of semicarbazide, extracting the lactone of 14-oXy-tetradecane-1- carboxylic acid by means of petroleum spirit. 5. The lactone from 14-oxy-tetradecane-1- carboxylic acid boiling at 176 degrees centigrade under 15 mm. pressure, solidifying into needles melting at 31-32 degrees centigrade and presenting the following characteristics: D 0.9447; m 1.4669.

whereof I affix my signature.

' In testimony LEOPOLD RUZICKA.