Method for the preparation of compounds having a 16-oxabicyclo[10.3.1]pentadecene scaffold and the subsequent products thereof

Abstract

The present invention relates to a method for preparing compounds having a 16-oxabicyclo[10.3.1]pentadecene skeleton, specifically 14-methyl-16-oxabicyclo[10.3.1]pentadecenes, and conversion products thereof.

Claims

1.-15. (canceled)

16. A method for preparing compounds of the general formula (I) ##STR00020## where R.sup.1 is hydrogen or C.sub.1-C.sub.4-alkyl, and conversion products thereof, wherein a) Providing a starting material comprising a compound of the general formula (II) ##STR00021## b) Subjecting the starting material provided in step a) in a reaction zone to a reaction at a temperature in a range from 100 to 240 C. and a pressure in a range from 0.1 to 150 mbar in the presence of a heterogeneous catalyst and a solvent or a solvent mixture having a vapor pressure in the range from 10.sup.5 to 100 mbar at 180 C., and c) Separating the compound of formula (I) from the reaction mixture by distillation.

17. The method according to claim 16, wherein R.sup.1 is hydrogen or methyl.

18. The method according to claim 16, wherein R.sup.1 is methyl.

19. The method according to claim 16, wherein the reaction in step b) comprises a first phase, during which the fraction not comprising any of the compound of formula (I) is separated from the reaction mixture by distillation.

20. The method according to claim 16, wherein the vapor pressure of the solvent used in step b) is less than the vapor pressure of diol (II).

21. The method according to claim 16, wherein the vapor pressure of the solvent used in step b) is between the vapor pressure of compound (I) and the vapor pressure of compound (II).

22. The method according to claim 16, wherein the vapor pressure of the solvent used in step b) is between the vapor pressure of compound (I) and the vapor pressure of compound (III) ##STR00022## where R.sup.1 is hydrogen or C.sub.1-C.sub.4-alkyl.

23. The method according to claim 16, wherein the solvent used in step b) is selected from the group consisting of aliphatic, cycloaliphatic and aromatic hydrocarbons, aliphatic, cycloaliphatic and aromatic monohydric and polyhydric alcohols, ether alcohols, polyether polyols and mono- and dialkyl ethers thereof, aromatic ethers and open-chain aliphatic ethers, ketones, esters, and mixtures thereof.

24. The method according to claim 16, wherein the solvent used in step b) is selected from the group consisting of C.sub.10-C.sub.30-alkanes, C.sub.6-C.sub.30-alkanols, C.sub.2-C.sub.30-alkanediols, polyalkylene glycols and mono- and dialkylethers thereof, and mixtures thereof.

25. The method according to claim 16, wherein the compound of formula (I.1) ##STR00023## is separated from the reaction mixture in step c) by one-stage distillation and the product separated comprises the following compounds, based in each case on the total weight of the separated product: 14-methyl-16-oxabicyclo[10.3.1]pentadecene (I.1): 75-95% by weight, 3-methylcyclopentadecane-1,5-diol (II.1): 0-5% by weight, 3-methylcyclopentadecane-1,5-dione (III.1): 1-10% by weight, 14-methyl-16-oxabicyclo[10.3.1]hexadecane (VI.1): 0-15% by weight.

26. The method according to claim 16, wherein the separation in step c) comprises a fractional distillation.

27. The method according to claim 26, wherein at least one distillation column having at least 10 theoretical plates is used for the separation by distillation of a fraction comprising the compound of formula (I) in step c).

28. The method according to claim 26 for preparing 14-methyl-16-oxabicyclo[10.3.1]pentadecene (I.1), wherein the compound of formula (I) is separated from the reaction mixture in step c) by fractional distillation and the product separated comprises the following compounds, based in each case on the total weight of the separated product: 14-methyl-16-oxabicyclo[10.3.1]pentadecene (I.1): 80-99% by weight, 3-methylcyclopentadecane-1,5-diol (II.1): 0-5% by weight, 3-methylcyclopentadecane-1,5-dione (III.1): 0 to 5% by weight, 14-methyl-16-oxabicyclo[10.3.1]hexadecane (VI.1): 0 to 15% by weight, solvent: 0 to 5% by weight, and 3-methylcyclopentadecan-5-ol-1-one (VII.1): 0-5% by weight.

29. The method according to claim 26 for preparing 14-methyl-16-oxabicyclo[10.3.1]pentadecene (I.1), wherein the compound of formula (I) is separated from the reaction mixture in step c) by fractional distillation and the product separated comprises the following compounds, based in each case on the total weight of the separated product: 14-methyl-16-oxabicyclo[10.3.1]pentadecene (I.1): 80-99% by weight, 3-methylcyclopentadecane-1,5-diol (II.1): 0-5% by weight, 3-methylcyclopentadecane-1,5-dione (III.1): preferably 0 to 1% by weight, 14-methyl-16-oxabicyclo[10.3.1]hexadecane (VI.1): 0 to 10% by weight, solvent: 0 to 1% by weight, and 3-methylcyclopentadecan-5-ol-1-one (VII.1): 0-5% by weight.

30. The method according to claim 16, wherein the solvent content of the reaction mixture in step b) is always maintained at least 20% by weight, based on the total weight of the reaction mixture in the reaction zone.

31. The method according to claim 16, wherein the solvent content of the reaction mixture in step b) is always maintained at least 30% by weight, based on the total weight of the reaction mixture in the reaction zone.

32. The method according to claim 16, wherein the solvent content of the reaction mixture in step b) is always maintained at least 50% by weight, based on the total weight of the reaction mixture in the reaction zone.

33. The method according to claim 16, wherein the method further comprises d) Subjecting the compounds of the general formula (I) to a reaction to obtain at least one compound of the general formula (IV) ##STR00024## where the symbol is in one case a single bond and in one case a double bond and R.sup.1 is hydrogen or C.sub.1-C.sub.4-alkyl.

34. The method according to claim 33, wherein the method further comprises e) Subjecting the compounds of the general formula (IV) to a hydrogenation to obtain the compound of the general formula (V) ##STR00025## where R.sup.1 is hydrogen or C.sub.1-C.sub.4-alkyl.

Description

DESCRIPTION OF FIGURES

[0218] FIG. 1 shows an apparatus which is in principle suitable for continuous, semi-continuous (semi-batch) or discontinuous (batch) modes of carrying out the method according to the invention. 3-Methylcyclopentadecane-1,5-diol is introduced into reactor R and is reacted in the presence of a heterogeneous catalyst. In the discontinuous mode of operation, 3-methylcyclopentadecane-1,5-diol is added prior to the start of the reaction. Optionally, after decline of the content of 3-methylcyclopentadecane-1,5-diol in reactor R below a certain threshold, fresh 3-methylcyclopentadecane-1,5-diol can be introduced into reactor R. This can be carried out both once and repeatedly. In the continuous mode of operation, 3-methylcyclopentadecane-1,5-diol is added depending on its consumption for preparing 14-methyl-16-oxabicyclo[10.3.1]pentadecene. The 14-methyl-16-oxabicyclo[10.3.1]pentadecene formed in reactor R is separated by distillation via column K and is condensed in a condenser linked with the heat exchanger W. A semi-continuous mode of operation is also possible, in which one of the steps, addition of 3-methylcyclopentadecane-1,5-diol or the separation of 14-methyl-16-oxa-bicyclo[10.3.1]pentadecene, is carried out continuously and the other in batch mode.

[0219] The examples which follow serve to illustrate the invention, but without restricting it in any way.

EXAMPLES

List of Compounds:

[0220] 14-methyl-16-oxabicyclo[10.3.1]pentadecene (I.1), [0221] 3-methylcyclopentadecane-1,5-diol (II.1), [0222] 3-methylcyclopentadecane-1,5-dione (III.1), [0223] 14-methyl-16-oxabicyclo[10.3.1]hexadecane (VI.1), [0224] 3-methylcyclopentadecan-5-ol-1-one (VII.1).

[0225] Gas chromatographic analyses were carried out in accordance with the following method: [0226] GC system: Agilent 7890 Series A [0227] Column: DB WAX 30 m (length)0.32 mm (internal diameter); [0228] FD 0.25 m (film); [0229] Injector temperature: 230 C.; detector temperature 280 C.; flow rate: 1.5 ml [0230] Temperature program: Starting temp.: 80 C. to 250 C. at 3 C./min, 250 C., 15 minutes isothermal.

[0231] The compounds present in the samples measured may have different isomers, for example, with respect to the position of the substituents on the ring system (cis,trans-isomers) and the position of the substituents on the double bonds. Insofar as these isomers have different retention times, the sum total of all determinable area integrals was generated for determining the amount of the compound concerned. The retention times are specified below.

Example 1

Comparative, Reaction without Added Solvent

[0232] 4.0 g of catalyst suspension (Raney copper, 30% in water) were initially charged in a 100 ml three-necked flask with 15.08 g of 3-methylcyclopentadecane-1,5-dial (II.1) (84.7 area % by GC). The pressure was initially reduced to 220 mbar at room temperature. The reaction mixture was then heated from room temperature to 166 C. and at the same time the pressure was reduced from 220 mbar to 40 mbar, whereupon the majority of the water of the catalyst suspension and also of the methanol distilled. After in-creasing the temperature to 172 to 176 C. and reducing the pressure to 1 to 2 mbar, the mixture was stirred for a further 5 h. The temperature was then increased to 180 C. and distillate was removed in one stage (without rectification) over 12 h. The head temperature was 165 C. at the start of the distillate collection and increased in the course of the distillation to 175 C. In total, 10 g of distillate were obtained. The content of 14-methyl-16-oxabicyclo[10.3.1]pentadecene (I.1) in the distillate was 10.6%, that of 3-methylcyclopentadecane-1,5-dione (III.1) was 27.7% and that of 3-methylcyclopentadecane-1,5-diol (II.1) was 8.3%. This corresponds to a yield of 9%.

Example 2

Inventive

[0233] 3 g of catalyst suspension (Raney copper, 50% in water) were washed three times with methanol. 10 g of 3-methylcyclopentadecane-1,5-diol (II.1) (82.5% by weight by GC) in 20 g of polyethylene glycol (ca. 8 PEG units, Lutrol E400 from BASF SE, vapor pressure at 180 C.: 0.02 mbar) were then initially charged at room temperature in a 100 ml three-necked flask together with the washed catalyst. The methanol and the residual water were distilled off slowly at 50 C. at a pressure of 250 to 3 mbar. The reaction mixture was then heated to 200 C. at a pressure of 20 mbar. The temperature was maintained for 16 hours. The pressure was then decreased to 1 mbar and the low-boiling components distilled off in one stage. Good mixing was ensured throughout the entire experiment by means of a magnetic stirrer. 4.5 g of distillate with a 14-methyl-16-oxa-bicyclo[10.3.1]pentadecene content of 87.2 area % by GC could be obtained, which corresponds to a yield of 52%. The 3-methylcyclopentadecane-1,5-diol content was 0.8 area % by GC and the 3-methylcyclopentadecane-1,5-dione content was 3.9 area % by GC.

Example 3

Inventive, Reaction Mixture Diluted with High-Boiling Solvent, which Boils Between 14-methyl-16-oxabicyclo[10.3.1]pentadecene and 3-methylcyclopentadecane-1,5-dione

[0234] 0.25 g of catalyst suspension (active Raney copper, 50% in water) were washed three times with methanol. 5 g of 3-methylcyclopentadecane-1,5-diol (II.1) (82.7 area % by GC) in 10 g of 1-hexadecanol (vapor pressure at 180 C.: 11 mbar) were then initially charged at room temperature in a 100 ml three-necked flask together with the washed catalyst. Good mixing was ensured throughout the entire experiment by means of a magnetic stirrer. The temperature was initially raised to 70 C. in order to melt the 1-hexadecanol. The methanol and the residual water were distilled off slowly at 70 C. The reaction mixture was then heated to 180 C. at a pressure of 40 mbar with constant stirring. The temperature was maintained for 20 hours. A sample was taken each time at 1, 3, 5 and 20 h and analyzed by GC. In Table 1 below, the contents of the 14-methyl-16-oxabicyclo[10.3.1]pentadecene (I.1) product of the 3-methylcyclopentadecane-1,5-diol (II.1) used and also of the compounds (III.1), (VI.1) and (VII.1) are given as area % by GC (GC area %) (without consideration of the 1-hexadecanol) as a function of the reaction time.

TABLE-US-00001 TABLE 1 Retention 22.75/22.95 20.7/27 40.5 43.5/44.8 50.8-52 time (I.1) (VI.1) (III.1) (VII.1) (II.1) [t/min] [GC area %] [GC area %] [GC area %] [GC area %] [GC area %] Reactant (0 h) 0.0 0.0 0.0 0 98.6 1 h 10.2 1.3 1.3 7.2 73.5 3 h 52.2 5.6 7.3 13.18 17.3 5 h 63.2 8.5 8.0 8.28 6.5 20 h 66.2 19.6 7.1 0 1.1

[0235] The pressure was then reduced to 1 mbar and the bottom temperature to 124 to 140 C. (see Table) and the low-boiling components could be distilled off in one stage. Three distillate fractions could be drawn off (Fr1: 0.6 g, Fr2: 1.3 g, Fr3: 7.3 g). All three fractions were solid and white.

TABLE-US-00002 TABLE 2 1- Hexa- Bottom Head (I.1) (VI.1) decanol (III.1) (II.1) temp. temp. Pressure [GC area [GC area [GC area [GC area [GC area Distillate C. C. mbar %] %] %] %] %] Fr1 124-127 111-114 1 62.25 4.7 22.88 0.87 1.03 Fr2 127-129 112-116 1 59.4 5.33 26.22 1.03 0 Fr3 128-140 116-128 1 15.79 4.16 75.76 2.73 0.34

[0236] Example 3 was repeated using nonadecane (vapor pressure at 180 C.: 11 mbar), tetradecanol (vapor pressure at 180 C.: 34 mbar), heptadecanol (vapor pressure at 180 C.: 7 mbar) and octadecanol (vapor pressure at 180 C.: 4 mbar) as solvent. In each case, product fractions with high 14-methyl-16-oxabicyclo[10.3.1]pentadecene content could be isolated.

Example 4

Inventive, Reaction Mixture Diluted with Hexadecanol, which Boils Between 14-methyl-16-oxabicyclo[10.3.1]pentadecene (I.1) and 3-methylcyclopentadecane-1,5-dione (III.1), 14-methyl-16-oxabicyclo[10.3.1]pentadecene was Distilled Off in Stages Together with Hexadecanol, 3-methylcyclopentadecane-1,5-diol (II.1) was Replaced with Hexadecanol

[0237] 0.5 g of catalyst suspension (active Raney copper, 50% in water) were washed three times with methanol. 10 g of 3-methylcyclopentadecane-1,5-diol (I1.1) (85.1 area % by GC) in 20 g of 1-hexadecanol (vapor pressure at 180 C.: 11 mbar) were then initially charged at room temperature in a 100 ml three-necked flask together with the washed catalyst. The temperature was initially raised to 70 C. in order to melt the 1-hexadecanol. The methanol and the residual water were distilled off slowly at 70 C. The reaction mixture was then heated to 180 C. at a pressure of 40 mbar. The temperature was maintained for 2 h. The temperature was then decreased to 145 C. and the pressure to 3 mbar and 7 g (Fraction 1) was distilled off in one stage. The distillate was analyzed and, based on the 14-methyl-16-oxabicyclo[10.3.1]pentadecene (I.1) drawn off, 3-methylcyclopentadecane-1,5-diol (II.1), together with 1-hexadecanol, was fed to the reactor so that a 3-methylcyclopentadecane-1,5-diol/1-hexadecanol ratio resulted as in the starting reaction mixture. The temperature was then increased again to 180 C. and the pressure to 40 mbar and maintained for 2 h. The pressure and the temperature were then decreased again to the values mentioned above and 4.5 g (fraction 2) and 4.8 g (fraction 3) were distilled. 3-Methylcyclopentadecane-1,5-diol (0.1) and 1-hexadecanol were again fed to the reactor. Using the same procedure as described above, a fourth fraction (fraction 4) of 10.8 g was generated. After the distillation of fraction 4, without further addition of 3-methylcyclopentadecane-1,5-diol and 1-hexadecanol, the reaction mixture was maintained at 180 C. and 40 mbar for a further 24 h and finally 5.1 g of distillate (fraction 5) were distilled off.

TABLE-US-00003 TABLE 3 1- Hexa- (I.1) (VI.1) decanol (VII.1) (II.1) [GC area [GC area [GC area (III.1) [GC area [GCarea %] %] %] [GC area %] %] %] Retention 22.5/22.6 26.7 34.1 40.1 43.2/44.5 50.8-52 time a) 0.0 0.0 0.0 0.0 0.0 95.3 b) 22.46 2.89 not integrated 9.68 25.59 28.12 c) 20.1 1.6 70.2 1.9 2.92 3.1 d) 15.1 4.7 not integrated 12.2 28.03 27.5 e) 12.3 3.0 not integrated 8.2 15.74 43.9 f) 39.4 4.3 42.5 1.5 0.8 1.4 g) 10.8 3.7 79.8 2.3 1.22 0.3 h) 11.2 4.4 not integrated 10.9 14.37 51.3 i) 5.9 2.5 not integrated 6.4 8.07 68.8 k) 10.6 3.0 81.9 1.2 0.36 2.7 l) 5.4 2.4 not integrated 5.3 3 79.2 m) 47.1 3.1 48.4 0.0 0 0.5 n) 40.7 14.1 not integrated 13.6 0 18.2 a) reactant (t = 0) b) bottoms prior to draw-off of fraction 1 c) fraction 1 b) bottoms after draw-off of fraction 1 e) bottoms after addition of 3-methylcyclopentadecane-1,5-dione (II.1)/1-hexadecanol f) fraction 2 g) fraction 3 h) bottoms after draw-off of fraction 3 i) bottoms after addition of 3-methylcyclopentadecane-1,5-dione (II.1)/1-hexadecanol k) fraction 4 l) bottoms after draw-off of fraction 4 m) fraction 5 n) bottoms after draw-off of fraction 5

Example 5

Inventive, Reaction Mixture Diluted with Solvent which Boils Between 14-methyl-16-oxabicyclo[10.3.1]pentadecene (II.1) and 3-methylcyclopentadecane-1,5-dione (III.1) and Also Draw-Off of 14-methyl-16-oxabicyclo[10.3.1]pentadecene (I.1) Via a Column

[0238] 1.5 g of catalyst suspension (active Raney copper, 50% in water) were washed three times with methanol. 30 g of 3-methylcyclopentadecane-1,5-diol (II.1) (95.2 area % by GC) in 60 g of 1-hexadecanol (vapor pressure at 180 C.: 11 mbar) were then initially charged at room temperature in a 100 ml three-necked flask together with the washed catalyst. A structured packing column was placed on the flask (structured packing bed height 53 cm, structured packing 3 mm Raschig rings, column internal diameter: 1.5 cm). The temperature was initially raised to 70 C. in order to melt the 1-hexadecanol. The methanol and the residual water were distilled off slowly at 70 C. The reaction mixture was then heated to 181 C. at 3 mbar top pressure with mixing by a magnetic stirrer. After 1 h, a distillate flow is set, wherein the distillate was initially collected at the top of the column under total reflux at 2 to 3 mbar top pressure. Over the next 2.5 h, a total of 10.6 g of distillate (fraction 1, Fr1) were taken off. Under constant conditions, further fractions were each taken after a further 3 h and 6 h (fraction 2, Fr2: 10.0 g, fraction 3, Fr3: 3.9 g). The hexadecanol content of all fractions was below 0.5%. The 14-methyl-16-oxabicyclo[10.3.1]pentadecene (I.1) content was 92% in fraction 1, 87% in fraction 2 and 57.8% in fraction 3. In total, this corresponds to a yield of 80%. 3-Methylcyclopentadecane-1,5-dione could not be detected in any of the fractions. The main by-product in the distillate was ether.

TABLE-US-00004 TABLE 4 (I.1) (VI.1) H-Hexadecanol [GC area %] [GC area %] [GC area %] Retention time 22.7/22.9 20.6 33.8 Fraction 1 92 2.6 0.4 Fraction 2 87 9.8 0.3 Fraction 3 57.8 42.3 0.4

Example 6

Inventive, Reaction Mixture Diluted with Solvent which Boils Between 14-methyl-16-oxabicyclo[10.3.1]pentadecene (I.1) and 3-methylcyclopentadecane-1,5-dione (III.1), Continuous Reaction Procedure with Feeding of and Also Continuous Draw-Off of 14-methyl-16-oxabicyclo[10.3.1]pentadecene (I.1) via a column

[0239] 2.25 g of catalyst (active Raney copper, distributed in water, withdrawal from fixed bed) were washed three times with methanol. 90 g of 3-methylcyclopentadecane-1,5-diol (II.1) (97.1% by weight by GC) in 180 g of 1-hexadecanol (vapor pressure at 180 C.: 11 mbar) were then initially charged at room temperature in a 500 ml three-necked flask together with the washed catalyst. A column with structured packings was placed on the flask (packing height 60 cm, structured packing Montz DN30 A3-1000). The temperature was initially raised to 70 C. in order to melt the 1-hexadecanol. The methanol and the residual water were distilled off slowly at 70 C. The reaction mixture was then heated to 180 C. at 3 mbar top pressure with mixing by a magnetic stirrer. After 1.5 h, a distillate flow is set, wherein the distillate was initially collected at the top of the column for 1 h under total reflux at 3 mbar top pressure.

[0240] Over the following days at a total experimental time of 156 h, at an average reflux ratio of 30, a total of 17 distillate fractions were taken off. The reflux ratio in this case was varied between 15 and 40 so that the top temperature remained constant at 134 C. It was ensured by means of varying the reflux ratio that no more product was removed from the reaction mixture than was formed by the reaction. The fractions and their composition can be taken from Table 1. By means of the continuous withdrawal of 14-methyl-16-oxabicyclo[10.3.1]pentadecene (I.1), the bottom temperature was also kept constant at 180 C. Therefore, the system is not depleted of 3-methylcyclopentadecane-1,5-dial (II.1), and as many equivalents of 3-methylcyclopentadecane-1,5-diol (II.1) were replaced as were drawn off of 14-methyl-16-oxabicyclo[10.3.1]pentadecene (I.1) and by-products. The addition of 3-methylcyclopentadecane-1,5-dial (II.1) was pulsed (portionwise). As the amount of distillate taken off was slowly diminished, a further 2.25 g of catalyst were added to the reactor after 24 and 89 hours in each case. The concentrations established in the reactor can be taken from Table 2. After 104 h, no further 3-methylcyclopentadecane-1,5-diol (II.1) was replaced and the residual 3-methylcyclopentadecane-1,5-diol (II.1) was converted to 14-methyl-16-oxabicyclo-[10.3.1]pentadecene (I.1). Over the whole experiment, a yield of 80% of 14-methyl-16-oxabicyclo[10.3.1]pentadecene (I.1) was apparent, based on 3-methylcyclopentadecane-1,5-diol (II.1). In total, 383 g of starting material having a 3-methylcyclopentadecane-1,5-diol content of 93.7% were fed.

TABLE-US-00005 TABLE 5 Overview of the fractions. All concentration data are area % by GC. (I.1) (VI.1) Time Amount [GC area %] [GC area %] Fraction [h] [g] Retention time 25.28 Retention time 29.18 1 10.8 35.9 90.7 4.3 2 24.5 13.3 83.2 8.1 3 32.0 24.2 58.9 30.9 4 38.0 20.9 66.4 24.1 5 45.5 25.4 54.0 35.8 6 53.5 7.8 88.3 2.7 7 60.5 15.5 93.1 1.3 8 68.5 22.2 94.4 1.2 9 75.2 17.9 92.0 2.0 10 81.8 12.9 93.3 1.6 11 97.0 35.4 96.0 0.5 12 104.3 22.1 95.4 0.6 13.sup.a) 143.2 62.4 86.0 5.1 .sup.a)= no further 3-methylcyclopentadecane-1,5-diol (II.1) replaced

TABLE-US-00006 TABLE 6 Overview of concentrations in the reactor. All data are area % by GC. 1-Hexa- (I.1) (VI.1) (III.1) (II.1) decanol [GC area [GC area [GC area [GC area [GC %] %] %] %] area %] Sam- Time Retention Retention Retention Retention Retention ple [h] time 25.28 time 29.18 time 42.76 time 53.55 time 36.18 1 10.8 0.3 1.9 1.1 28.8 66.5 2 24.5 0.2 3.1 1.5 13.9 79.0 3 32.0 0.0 2.3 1.3 30.5 63.5 4 38.0 0.1 1.4 1.4 26.4 66.2 5 53.5 1.8 3.1 1.3 35.1 52.4 6 75.2 1.3 3.1 1.6 30.7 54.2 7 89.0 7.9 1.7 1.6 29.0 48.3 8 130.2 3.4 4.7 2.8 17.2 53.5 9 155.7 0.0 5.2 5.3 1.4 50.2