Perfluorotricyclic amines as oxygen carriers

Abstract

A novel compound of the formula, ##STR1## wherein k, j, l and m are zero or an integer of from 1 to 3, and n is an integer of from 1 to 3, the rings A, B and C being optionally substituted with at least one trifluoromethyl group, prepared by reacting the corresponding perhydro compound with fluorine is useful as a material capable of carrying oxygen in an aqueous emulsion for lifesaving a patient suffering from massive hemorrhage and for preserving internal organs in transplantation.

Description

This invention relates to a novel perfluorotricyclic amine compound useful as an oxygen carrier in artificial blood or in an infusion fluid.

More particularly, it relates to a perfluorotricyclic amine compound represented by the general formula ##STR2## wherein k, j, l and m are zero or an integer of from 1 to 3, and n is an integer of from 1 to 3, the rings A, B and C being optionally substituted with at least one trifluoromethyl group.

Regarding the general formula (I), it is preferable that the ring A is selected from five- to seven-membered rings, the ring B from five- to eight-membered rings, and the ring C from five- to eight-membered rings. The total number of the carbon atoms contained in the compound of formula (I) is preferably from 9 to 12.

In detail, the first series of the present perfluorotricyclic amine compounds without optional substituent of --CF.sub.3 is represented by the formula, ##STR3## wherein k is an integer of 1 or 2; l, m and n are zero or an integer of 1 or 2. The compound has preferably 10 to 12 carbon atoms in total.

The second series is also represented by the formula, ##STR4## wherein k and n are an integer of 1, 2 or 3; l and m are zero or an integer of 1, 2 or 3. The compound has preferably 10 to 12 carbon atoms in total.

The third series is also represented by the formula, ##STR5## wherein k and j are zero or an integer of 1; l, m and n are zero or an integer of 1 or 2. The compound has preferably 10 to 12 carbon atoms in total.

The fourth series is also represented by the formula, ##STR6## wherein l and m are zero or an integer of 1, 2 or 3; n is an integer of 1, 2 or 3.

The compound may have at most two trifluoromethyl groups and its total number of carbon atoms are preferably 9 to 12 in case of no substituent and 10 to 11 depending on the substituted number of the trifluoromethyl group.

The compound of formula (I) can be prepared by fluorinating a perhydro-compound corresponding to the compound of formula (I). The methods of fluorination include, for example, a direct fluorination, a fluorination by use of cobalt trifluoride, and an electro chemical fluorination.

The preparation of the compound of formula (I) of this invention is preferably performed by the electrochemical fluorination method. This is performed, for example, by mixing anhydrous hydrogen fluoride and the perhydro-compound used as the starting compound in an electrolytic cell and subjecting the resulting solution to electrolysis. The voltage, the current density at the anode, and the temperature of electrolytic solution are normally 3-9 V, 0.1-10 A/dm.sup.2 and 4.degree.-12.degree. C., respectively.

The compound of formula (I) thus formed was drained from the bottom of the cell, being insoluble in anhydrous hydrogen fluoride.

The isolation and purification of the compound from the drained product are carried out, for example, by adding a mixture of equal volumes of an aqueous caustic alkaline solution and an amine compound to the drained product and refluxing to decompose partially fluorinated compounds. After cooled, the lowermost layer containing the desired compound of formula (I) is separated, washed with an aqueous acetone solution containing a suitable amount of potassium iodide to remove perfluoroalkyl nitrogen fluorides, and subjected to fractional distillation to obtain the fraction of the desired compound of formula (I).

Since the compound of the formula (I) of this invention can not only dissolve a large amount of oxygen, and is chemically and biologically inert, but also it can be excreted rapidly from the body, it can form, for example, an aqueous emulsion containing 5 to 50, preferably 10-40, % (W/V) of the compound of formula (I) to be used as an oxygen carrier in an artificial blood or in an infusion liquid for men and other mammals such as dogs, cats, cattle, mice, rats and guinea pigs.

The symbol "%(W/V)" referred to herein mean the amount of the material by weight (gram) based on 100 ml of the resulting emulsion.

In the preparation of the emulsion mentioned above, there used, as an emulsifier, a nonionic surfactant and/or phospholipids in an added amount of 1 to 5% (W/V).

As the medium for the emulsion, a physiologically acceptable aqueous solution is employed. If necessary, there may be added thereto such materials as glycerol to provide the desired isotonicity, and such plasma expanders as HES or dextran to regulate the colloid osmotic pressure of the emulsion.

The emulsion can be prepared by mixing the above-mentioned ingredients and homogenizing the mixture by means of, for example, a high-pressure jet type homogenizer until the particle diameters become 0.05 to 0.3 .mu.m, preferably less than 0.2 .mu.m.

The perhydro-compounds (starting compounds) corresponding to the compounds of formula (I) are substantially known already.

EXAMPLE 1

Into an electrolytic cell made of Monel metal with an inner volume of 1.5 l, which is provided with electrode plates (six plates as anode and seven plates as cathode) made of nickel (purity: 99.6% or higher) arranged alternately with an inter-electrode distance of 1.7-2.0 mm, the effective anode surface area being 10.5 dm.sup.2, and with a reflux condenser made of copper at the upper part of the cell, was introduced 1.2 l of anhydrous hydrogen fluoride, and trace amounts of impurities present in the system (moisture and sulfuric acid) were removed by preliminary electrolysis. Then, 0.86 mol (130 g) of 2-azatricyclo[5,3,1,0.sup.2,6 ]-undecane was dissolved into the anhydrous hydrogen fluoride, and electrolysis was carried out, while introducing helium gas from the bottom of the cell at a rate of 100 ml/min., under the conditions of anode current density of 0.4-2.0 A/dm.sup.2, voltage of 5-9 V and solution 7.degree.-12.degree. C., until the electrolytic voltage had reached 9.0 V. The ampere-hours amounted to 975. Hydrogen fluoride was added at a rate of 250 ml per 24 hours during the electrolysis. No attempt was made to collect volatile products formed by a bond breaking reaction, which would give more yields of the desired product. After completion of the electrolysis, fluorocarbons in the lower layer in the cell was drained through the bottom of the cell, weighed 265 g (58% yield).

To the fluorocarbons thus separated, were added equal volumes of 70% aqueous potassium hydroxide solution and diisobutylamine, and the resulting mixture was refluxed for about five days. The reaction mixture was then cooled in an ice bath, and filtered by suction. The perfluoro-compounds sedimented in the lowermost layer were separated in a separatory funnel, washed successively with diluted sulfuric acid, concentrated sulfuric acid, saturated aqueous sodium hydrogen carbonate solution, 90% aqueous acetone solution containing 3% of potassium iodide, and water to yield 110 g of a transparent perfluoro-compounds containing no protons. This was distilled on a fractional distillation apparatus equipped with a spinning band column to afford 33 g (7% yield) of the desired product boiling at 143.degree.-152.degree. C. This product was collected, purified, and then analyzed by infrared absorption spectrometry, .sup.19 F-nuclear magnetic resonance spectrometory and mass spectrometory, and was confirmed to be the objective compound, perfluoro-2-azatricyclo[5,3,1,0.sup.2,6 ]-undecane of which chemical structure is shown in Table 1 as compound No. 1.

EXAMPLES 2-134

A series of other perfluorotricyclic amine compounds having the formulas (II and V), wherein j is 1 was synthesized from perhydrotricyclic amine compounds each corresponding thereto and purified in the same manner as that described above and each product was confirmed to be the objective compound upon analysis by infrared absorption spectrometory, .sup.19 F-nuclear magnetic resonance spectrometory and mass spectrometory.

The structural formula and the boiling point of each of the objective compounds as well as the starting compounds are shown in the Table 1. The symbol "F-" in the structural formula indicates that the compound is perfluorinated. For example, the formula ##STR7## indicates in its exact meaning the formula ##STR8##

TABLE 1______________________________________ Boil- ing Starting Objective pt.No. compound compound (.degree.C.)______________________________________1 2-Azatricyclo- [5,3,1,0.sup.2,6 ]- undecane 143- 1522 1-Methyl-2-aza- tricyclo[5,3,1, 0.sup.2,6 ]undecane ##STR9## 154- 165 3 3-Methyl-2-aza- tricyclo[5,3,1, 0.sup.2,6 ]undecane ##STR10## 156- 166 4 4-Methyl-2-aza- tricyclo[5,3,1, 0.sup.2,6 ]undecane ##STR11## 156- 167 5 5-Methyl-2-aza- tricyclo[5,3,1, 0.sup.2,6 ]undecane ##STR12## 156- 167 6 6-Methyl-2-aza- tricyclo[5,3,1, 0.sup.2,6 ]undecane ##STR13## 155- 166 7 7-Methyl-2-aza- tricyclo[5,3,1, 0.sup.2,6 ]undecane ##STR14## 155- 167 8 8-Methyl-2-aza- tricyclo[5,3,1, 0.sup.2,6 ]undecane ##STR15## 156- 167 9 9-Methyl-2-aza- tricyclo[5,3,1, 0.sup.2,6 ]undecane ##STR16## 156- 167 10 10-Methyl-2-aza- tricyclo[5,3,1, 0.sup.2,6 ]undecane ##STR17## 156- 168 11 11-Methyl-2-aza- tricyclo[5,3,1, 0.sup.2,6 ]undecane ##STR18## 155- 166 12 2-Azatricyclo- [6,3,1,0.sup.2,7 ]- dodecane ##STR19## 154- 166 13 2-Azatricyclo- [6,3,1,0.sup.2,6 ]- dodecane ##STR20## 155- 166 14 3-Azatricyclo- [6,3,1,0.sup.3,7 ]- dodecane ##STR21## 155- 166 15 2-Azatricyclo- [7,3,1,0.sup.2,6 ]- tridecane ##STR22## 167- 177 16 2-Azatricyclo- [7,3,1,0.sup.2,7 ]- tridecane ##STR23## 167- 177 17 2-Azatricyclo- [7,3,1,0.sup.2,8 ]- tridecane ##STR24## 167- 177 18 3-Azatricyclo- [7,3,1,0.sup.3,7 ]- tridecane ##STR25## 166- 176 19 3-Azatricyclo- [7,3,1,0.sup.3,8 ]- tridecane ##STR26## 167- 177 20 4-Azatricyclo- [7,3,1,0.sup.4,8 ]- tridecane ##STR27## 167- 177 21 2-Azatricyclo- [6,4,0,1.sup.2,6 ]- dodecane ##STR28## 155- 167 22 2-Azatricyclo- [6,4,1,0.sup.2,7 ]- tridecane ##STR29## 167- 178 23 2-Azatricyclo- [6,4,0,1.sup.2,7 ]- tridecane ##STR30## 167- 177 24 3-Azatricyclo- [6,4,0,1.sup.3,8 ]- tridecane ##STR31## 167- 177 25 2-Azatricyclo- [6,2,1,2.sup.2,7 ]- undecane ##STR32## 143- 153 26 1-Methyl-2-aza- tricyclo[6,2,1, 0.sup.2,7 ]undecane ##STR33## 155- 165 27 3-Methyl-2-aza- tricyclo[6,2,1, 0.sup.2,7 ]undecane ##STR34## 156- 166 28 4-Methyl-2-aza- tricyclo[6,2,1, 0.sup.2,7 ]-undecane ##STR35## 156- 167 29 5-Methyl-2-aza- tricyclo[6,2,1, 0.sup.2,7 ]undecane ##STR36## 155- 167 30 6-Methyl-2-aza- tricyclo[6,2,1, 0.sup.2,7 ]undecane ##STR37## 156- 166 31 7-Methyl-2-aza- tricyclo[6,2,1, 0.sup.2,7 ]undecane ##STR38## 155- 166 32 8-Methyl-2-aza- tricyclo[6,2,1, 0.sup.2,7 ]undecane ##STR39## 155- 165 33 9-Methyl-2-aza- tricyclo[6,2,1, 0.sup.2,7 ]-undecane ##STR40## 156- 166 34 10-Methyl-2-aza- tricyclo[6,2,1, 0.sup.2,7 ]undecane ##STR41## 156- 166 35 11-Methyl-2-aza- tricyclo[6,2,1, 0.sup.2,7 ]undecane ##STR42## 155- 167 36 2-azatricyclo- [6,2,1,0.sup.2,6 ]- undecane ##STR43## 143- 153 37 1-Methyl-2-aza- tricyclo[ 6,2,1, 0.sup.2,6 ]undecane ##STR44## 155- 166 38 3-Methyl-2-aza- tricyclo[6,2,1, 0.sup.2,6 ]undecane ##STR45## 156- 166 39 4-Methyl-2-aza- tricyclo[6,2,1, 0.sup.2,6 ]undecane ##STR46## 156- 167 40 5-Methyl-2-aza- tricyclo[6,2,1, 0.sup.2,6 ]undecane ##STR47## 156- 167 41 6-Methyl-2-aza- tricyclo[6,2,1, 0.sup.2,6 ]undecane ##STR48## 155- 166 42 7-Methyl-2-aza- tricyclo[6,2,1, 0.sup.2,6 ]undecane ##STR49## 155- 166 43 8-Methyl-2-aza- tricyclo[6,2,1, 0.sup.2,6 ]undecane ##STR50## 155- 166 44 9-Methyl-2-aza- tricyclo[6,2,1, 0.sup.2,6 ]undecane ##STR51## 156- 166 45 10-Methyl-2-aza- tricyclo[6,2,1, 0.sup.2,6 ]undecane ##STR52## 156- 167 46 11-Methyl-2-aza- tricyclo[6,2,1, 0.sup.2,6 ]undecane ##STR53## 156- 167 47 3-Azatricyclo- [6,2,1,0.sup.3,7 ]- undecane ##STR54## 143- 154 48 1-Methyl-3-aza- tricyclo[6,2, 1,0.sup.3,7 ]undecane ##STR55## 156- 166 49 2-Methyl-3-aza- tricyclo[6,2,1, 0.sup.3,7 ]undecane ##STR56## 157- 167 50 4-Methyl-3-aza- tricyclo[6,2,1, 0.sup.3,7 ]undecane ##STR57## 157- 166 51 5-Methyl-3-aza- tricyclo[6,2,1, 0.sup.3,7 ]undecane ##STR58## 157- 167 52 6-Methyl-3-aza- tricyclo[6,2,1, 0.sup.3,7 ]undecane ##STR59## 157- 167 53 7-Methyl-3-aza- tricyclo[6,2,1, 0.sup.3,7 ]undecane ##STR60## 156- 166 54 8-Methyl-3-aza- tricyclo[6,2,1, 0.sup.3,7 ]undecane ##STR61## 156- 167 55 9-Methyl-3-aza- tricyclo[6,2,1, 0.sup.3,7 ]undecane ##STR62## 157- 166 56 10-Methyl-3-aza- tricyclo[6,2,1, 0.sup.3,7 ]undecane ##STR63## 157- 167 57 11-Methyl-3-aza- tricyclo[6,2,1, 0.sup.3,7 ]undecane ##STR64## 157- 166 58 2-Azatricyclo- [7,2,1,0.sup.2,6 ]- dodecane ##STR65## 156- 167 59 2-Azatricyclo- [7,2,1,0.sup.2,7 ]- dodecane ##STR66## 156- 166 60 2-Azatricyclo- [7,2,1,0.sup.2,8 ]- dodecane ##STR67## 156- 166 61 3-Azatricyclo- [7,2,1,0.sup.3,7 ]- dodecane ##STR68## 155- 165 62 3-Azatricyclo- [7,2,1,0.sup.3,8 ]- dodecane ##STR69## 156- 166 63 4-Azatricyclo- [7,2,1,0.sup.4,8 ]- dodecane ##STR70## 155- 166 64 2-Azatricyclo- [8,2,1,0.sup.2,6 ]- tridecane ##STR71## 168- 177 65 2-Azatricyclo- [8,2,1,0.sup.2,7 ]- tridecane ##STR72## 167- 177 66 2-Azatricyclo- [8,2,1,0.sup.2,8 ]- tridecane ##STR73## 167- 178 67 2-Azatricyclo- [8,2,1,0.sup.2,9 ]- tridecane ##STR74## 166- 178 68 3-Azatricyclo- [8,2,1,0.sup.3,7 ]- tridecane ##STR75## 167- 178 69 3-Azatricyclo- [8,2,1,0.sup.3,8 ]- tridecane ##STR76## 166- 177 70 3-Azatricyclo- [8,2,1,0.sup.3,9 ]- tridecane ##STR77## 167- 177 71 4-Azatricyclo- [8,2,1,0.sup.4,8 ]- tridecane ##STR78## 167- 178 72 4-Azatricyclo- [8,2,1,0.sup.4,9 ]- tridecane ##STR79## 167- 177 73 5-Azatricyclo- [8,2,1,0.sup.5,9 ]- tridecane ##STR80## 166- 176 74 2-Azatricyclo- [5,2,1,0.sup.2,6 ]- decane ##STR81## 120- 130 75 1-Methyl-2-aza- tricyclo[5,2,1, 0.sup.2,6 ]-decane ##STR82## 142- 153 76 3-Methyl-2-aza- tricyclo[5,2,1, 0.sup.2,6 ]decane ##STR83## 143- 153 77 4-Methyl-2-aza- tricyclo[5,2,1, 0.sup. 2,6 ]decane ##STR84## 143- 154 78 5-methyl-2-aza- tricyclo[5,2,1, 0.sup.2,6 ]decane ##STR85## 143- 154 79 6-Methyl-2-aza- tricyclo[5,2,1, 0.sup.2,6 ]decane ##STR86## 142- 153 80 7-Methyl-2-aza- tricyclo[5,2,1, 0.sup.2,6 ]decane ##STR87## 142- 154 81 8-Methyl-2-aza- tricyclo[5,2,1, 0.sup.2,6 ]decane ##STR88## 143- 154 82 9-Methyl-2-aza- tricyclo[5,2,1, 0.sup.2,6 ]decane ##STR89## 143- 154 83 10-Methyl-2-aza- tricyclo[5,2,1, 0.sup.2,6 ]decane ##STR90## 144- 154 84 1-Ethyl-2-aza- tricyclo[5,2,1, 0.sup.2,6 ]decane ##STR91## 156- 167 85 3-Ethyl-2-aza- tricyclo[5,2,1, 0.sup.2,6 ]decane ##STR92## 157- 168 86 4-Ethyl-2-aza- tricyclo[5,2,1, 0.sup.2,6 ]decane ##STR93## 157- 167 87 5-Ethyl-2-aza- tricyclo[5,2,1, 0.sup.2,6 ]decane ##STR94## 157- 167 88 6-Ethyl-2-aza- tricyclo[5,2,1, 0.sup.2,6 ]decane ##STR95## 156- 166 89 7-Ethyl-2-aza- tricyclo[5,2,1, 0.sup.2,6 ]decane ##STR96## 156- 166 90 8-Ethyl-2-aza- tricyclo[5,2,1, 0.sup.2,6 ]decane ##STR97## 157- 168 91 9-Ethyl-2-aza- tricyclo[5,2,1, 0.sup.2,6 ]decane ##STR98## 157- 167 92 10-Ethyl-2-za- tricyclo[5,2,1, 0.sup.2,6 ]decane ##STR99## 157- 167 93 1,3-Dimethyl-2- azatricyclo- [5,2,1,0.sup.2,6 ]- decane ##STR100## 156- 167 94 1,4-Dimethyl-2- azatricyclo- [5,2,1,0.sup.2,6 ]- decane ##STR101## 156- 167 95 1,5-Dimethyl-2- azatricyclo- [5,2,1,0.sup.2,6 ]- decane ##STR102## 156- 168 96 1,6-Dimethyl-2- azatricyclo- [5,2,1,0.sup.2,6 ]- decane ##STR103## 155- 165 97 1,7-Dimethyl-2- azatricyclo- [5,2,1,0.sup.2,6 ]- decane ##STR104## 155- 166 98 1,8-Dimethyl-2- azatricyclo- [ 5,2,1,0.sup.2,6 ]- decane ##STR105## 156- 167 99 1,9-Dimethyl-2- azatricyclo- [5,2,1,0.sup.2,6 ]- decane ##STR106## 156- 167 100 1,10-Dimethyl-2- azatricyclo- [5,2,1,0.sup.2,6 ]- decane ##STR107## 156- 167 101 3,3-Dimethyl-2- azatricyclo- [5,2,1,0.sup.2,6 ]- decane ##STR108## 157- 167 102 3,4-Dimethyl-2- azatricyclo- [5,2,1,0.sup.2,6 ]- decane ##STR109## 157- 167 103 3,5-Dimethyl-2- azatricyclo- [5,2,1,0.sup.2,6 ]- decane ##STR110## 157- 167 104 3,6-Dimethyl-2- azatricyclo- [5,2,1,0.sup.2,6 ]- decane ##STR111## 156- 166 105 3,7-Dimethyl-2- azatricyclo- [5,2,1,0.sup.2,6 ]- decane ##STR112## 156- 167 106 3,8-Dimethyl-2- azatricyclo- [5,2,1,0.sup.2,6 ]- decane ##STR113## 156- 167 107 3,9-Dimethyl-2- azatricyclo- [5,2,1,0.sup.2,6 ]- decane ##STR114## 157- 167 108 3,10-Dimethyl-2- azatricyclo- [5,2,1,0.sup.2,6 ]- decane ##STR115## 157- 166 109 4,4-Dimethyl-2- azatricyclo- [5,2,1,0.sup.2,6 ]- decane ##STR116## 157- 167 110 4,5-Dimethyl-2- azatricyclo- [5,2,1,0.sup.2,6 ]- decane ##STR117## 156- 167 111 4,6-Dimethyl-2- azatricyclo- [5,2,1,0.sup.2,6 ]- decane ##STR118## 156- 165 112 4,7-Dimethyl-2- azatricyclo- [5,2,1,0.sup.2,6 ]- decane ##STR119## 155- 166 113 4,8-Dimethyl-2- azatricyclo- [5,2,1,0.sup.2,6 ]- decane ##STR120## 156- 167 114 4,9-Dimethyl-2- azatricyclo- [5,2,1,0.sup.2,6 ]- decane ##STR121## 156- 167 115 4,10-Dimethyl-2- azatricyclo- [5,2,1,0.sup.2,6 ]- decane ##STR122## 156- 166 116 5,5-Dimethyl-2- azatricyclo- [5,2,1,0.sup.2,6 ]- decane ##STR123## 156- 167 117 5,6-Dimethyl-2- azatricyclo- [5,2,1,0.sup.2,6 ]- decane ##STR124## 155- 166 118 5,7-Dimethyl-2- azatricyclo- [5,2,1,0.sup.2,6 ]- decane ##STR125## 154- 166 119 5,8-Dimethyl-2- azatricyclo- [5,2,1,0.sup.2,6 ]- decane ##STR126## 157- 168 120 5,9-Dimethyl-2- azatricyclo- [5,2,1,0.sup.2,6 ]- decane ##STR127## 157- 167 121 5,10-Dimethyl-2- azatricyclo- [5,2,1,0.sup.2,6 ]- decane ##STR128## 156- 167 122 6,7-Dimethyl-2- azatricyclo- [5,2,1,0.sup.2,6 ]- decane ##STR129## 154- 166 123 6,8-Dimethyl-2- azatricyclo- [5,2,1,0.sup.2,6 ]- decane ##STR130## 155- 167 124 6,9-Dimethyl-2- azatricyclo- [5,2,1,0.sup.2,6 ]- decane ##STR131## 155- 166 125 6,10-Dimethyl-2- azatricyclo- [5,2,1,0.sup.2,6 ] - decane ##STR132## 156- 165 126 7,8-Dimethyl-2- azatricyclo- [5,2,1,0.sup.2,6 ]- decane ##STR133## 156- 167 127 7,9-Dimethyl-2- azatricyclo- [5,2,1,0.sup.2,6 ]- decane ##STR134## 155- 167 128 7,10-Dimethyl-2- azatricyclo- [5,2,1,0.sup.2,6 ]- decane ##STR135## 154- 166 129 8,8-Dimethyl-2- azatricyclo- [5,2,1,0.sup.2,6 ]- decane ##STR136## 156- 165 130 8,9-Dimethyl-2- azatricyclo- [5,2,1,0.sup.2,6 ]- decane ##STR137## 155- 166 131 8,10-Dimethyl-2- azatricyclo- [5,2,1,0.sup.2,6 ]- decane ##STR138## 156- 166 132 9,9-Dimethyl-2- azatricyclo- [5,2,1,0.sup.2,6 ]- decane ##STR139## 155- 166 133 9,10-Dimethyl-2- azatricyclo- [5,2,1,0.sup.2,6 ]- decane ##STR140## 156- 166 134 10,10-Dimethyl-2- azatricyclo- [5,2,1,0.sup.2,6 ]- decane ##STR141## 156- 165______________________________________

EXAMPLES 135-157

A series of perfluorotricyclic amine compounds of the formula (IV) wherein j is 2 or 3 was synthesized, purified and confirmed to be the objective compound in the same manner as in Example 1.

The structural formula and the boiling point of each of the objective compounds are shown in the Table 2. The symbol "F-" in the structural formula indicates that the compound is perfluorinated. For example, the formula ##STR142## indicates in its exact meaning the formula ##STR143##

TABLE 2______________________________________ Starting Objective BoilingNo. compound compound pt. (.degree.C.)______________________________________135 2-Azatricyclo- [5,2,2,0.sup.2,6 ]- undecane 144-155136 1-Methyl-2-aza- tricyclo[5,2,2, 0.sup.2,6 ]undecane ##STR144## 155-166 137 3-Methyl-2-aza- tricyclo[5,2,2, 0.sup.2,6 ]undecane ##STR145## 156-167 138 4-Methyl-2-aza- tricyclo[5,2,2, 0.sup.2,6 ]undecane ##STR146## 156-167 139 5-Methyl-2-aza- tricyclo[5,2,2, 0.sup.2,6 ]undecane ##STR147## 156-168 140 6-Methyl-2-aza- tricyclo[5,2,2 0.sup.2,6 ]undecane ##STR148## 155-166 141 7-Methyl-2-aza- tricyclo[5,2,2, 0.sup.2,6 ]undecane ##STR149## 155-165 142 8-Methyl-2-aza- tricyclo[5,2,2, 0.sup.2,6 ]undecane ##STR150## 156-167 143 9-Methyl-2-aza- tricyclo[5,2,2, 0.sup.2,6 ]undecane ##STR151## 156-167 144 2-Azatricyclo- [6,2,2,0.sup.2,7 ]- dodecane ##STR152## 155-165 145 2-Azatricyclo- [6,2,2,0.sup.2,6 ]- dodecane ##STR153## 156-166 146 3-Azatricyclo- [6,2,2,0.sup.3,7 ]- dodecane ##STR154## 156-166 147 2-Azatricyclo- [7,2,2,0.sup.2,6 ]- tridecane ##STR155## 167-176 148 2-Azatricyclo- [7,2,2,0.sup.2,7 ]- tridecane ##STR156## 166-177 149 2-Azatricyclo- [7,2,2,0.sup.2,8 ]- tridecane ##STR157## 165-176 150 3-Azatricyclo- [7,2,2,0.sup.3,7 ]- tridecane ##STR158## 166-177 151 3-Azatricyclo- [7,2,2,0.sup.3,8 ]- tridecane ##STR159## 166-176 152 4-Azatricyclo- [7,2,2,0.sup.4,8 ]- tridecane ##STR160## 164-177 153 2-Azatricyclo- [5,3,2,0.sup.2,6 ]- dodecane ##STR161## 156-165 154 2-Azatricyclo- [6,3,2,0.sup.2,6 ] - tridecane ##STR162## 166-176 155 2-Azatricyclo- [6,3,2,0.sup.2,7 ]- tridecane ##STR163## 166-176 156 3-Azatricyclo- [6,3,2,0.sup.3,7 ]- tridecane ##STR164## 166-177 157 2-Azatricyclo- [5,3,3,0.sup.2,6 ]- tridecane ##STR165## 165-176______________________________________

EXAMPLES 158-201

A series of perfluorotricyclic amine compounds of the formula (III) wherein j is zero was synthesized, purified and confirmed to be the objective compound in the same manner as in Example 1.

The structural formula and the boiling point of each of the objective compounds is shown in the Table 3. The symbol "F-" in the structural formula indicates that the compound is perfluorinated. For example, the formula ##STR166## indicates in its exact meaning the formula ##STR167##

TABLE 3______________________________________ Boil- ing Starting Objective pt.No. compound compound (.degree.C.)______________________________________158 1-Azatricyclo- [6,3,0,0.sup.2,6 ]- undecane 143- 153159 2-Methyl-1-aza- tricyclo[6,3,0, 0.sup.2,6 ]undecane ##STR168## 155- 165 160 3-Methyl-1-aza- tricyclo[6,3,0, 0.sup.2,6 ]undecane ##STR169## 155- 166 161 4-Methyl-1-aza- tricyclo[6,3,0, 0.sup.2,6 ]undecane ##STR170## 156- 166 162 5-Methyl-1-aza- tricyclo[6,3,0, 0.sup.2,6 ]undecane ##STR171## 155- 166 163 6-Methyl-1-aza- tricyclo[6,3,0, 0.sup.2,6 ]undecane ##STR172## 155- 165 164 7-Methyl-1-aza- tricyclo[6,3,0, 0.sup.2,6 ]undecane ##STR173## 156- 166 165 8-Methyl-1-aza- tricyclo[6,3,0, 0.sup.2,6 undecane ##STR174## 154- 166 166 9-Methyl-1-aza- tricyclo[6,3,0, 0.sup.2,6 ]undecane ##STR175## 155- 165 167 10-Methyl- 1-aza- tricyclo[6,3,0, 0.sup.2,6 ]undecane ##STR176## 155- 165 168 11-Methyl- 1-aza- tricyclo[6,3,0, 0.sup.2,6 ]undecane ##STR177## 155- 166 169 1-Azatricyclo- [6,3,0,0.sup.3,7 ]- undecane ##STR178## 143- 154 170 2-Methyl-1-aza- tricyclo- [6,3,0,0.sup.3,7 ]- undecane ##STR179## 156- 166 171 3-Methyl-1-aza- tricyclo- [6,3,0,0.sup.3,7 ]- undecane ##STR180## 154- 165 172 4-Methyl-1-aza- tricyclo- [6,3,0,0.sup.3,7 ]- undecane ##STR181## 155- 165 173 5-Methyl-1-aza- tricyclo- [6,3,0,0.sup.3,7 ]- undecane ##STR182## 155- 165 174 6-Methyl-1-aza- tricyclo- [6,3,0,0.sup.3,7]- undecane ##STR183## 155- 166 175 7-Methyl-1-aza- tricyclo- [6,3,0,0.sup.3,7 ]- undecane ##STR184## 154- 165 176 8-Methyl-1-aza- tricyclo- [6,3,0,0.sup.3,7 ]- undecane ##STR185## 154- 166 177 9-Methyl-1-aza- tricyclo- [6,3,0,0.sup.3,7 ]- undecane ##STR186## 156- 166 178 10-Methyl- 1-aza- tricyclo- [6,3,0,0.sup.3,7 ]- undecane ##STR187## 155- 165 179 11-Methyl- 1-aza- tricyclo- [6,3,0,0.sup.3,7 ]- undecane ##STR188## 155- 164 180 1-Azatricyclo- [7,3,0,0.sup.2,7 ]- dodecane ##STR189## 154- 165 181 1-Azatricyclo- [7,3,0,0.sup.2,6 ]- dodecane ##STR190## 155- 165 182 1-Azatricyclo- [7,3,0,0.sup.3,7 ]- dodecane ##STR191## 155- 166 183 1-Azatricyclo- [7,3,0,0.sup.3,8 ]- dodecane ##STR192## 154- 165 184 1-Azatricyclo- [7,3,0,0.sup.4,8 ]- dodecane ##STR193## 153- 165 185 2-Azatricyclo- [7,3,0,0.sup.2,7 ]- dodecane ##STR194## 154- 165 186 3-Azatricyclo- [7,3,0,0.sup.3,8 ]- dodecane ##STR195## 154- 165 187 1-Azatricyclo- [8,3,0,0.sup.2,8 ]- tridecane ##STR196## 166- 177 188 1-Azatricyclo- [8,3,0,0.sup.2,7 ]- tridecane ##STR197## 165- 177 189 1-Azatricyclo- [8,3,0,0.sup.2,6 ]- tridecane ##STR198## 166- 176 190 1-Azatricyclo- [8,3,0,0.sup.3,9 ]- tridecane ##STR199## 166- 176 191 1-Azatricyclo- [8,3,0,0.sup.3,8 ]- tridecane ##STR200## 165- 175 192 1-Azatricyclo- [8,3,0,0.sup.3,7 ]- tridecane ##STR201## 166- 176 193 1-Azatricyclo- [8,3,0,0.sup.4,9 ]- tridecane ##STR202## 165- 176 194 1-Azatricyclo- [8,3,0,0.sup.4,8 ]- tridecane ##STR203## 165- 175 195 1-Azatricyclo- [7,4,0,0.sup.2,7 ]- tridecane ##STR204## 164- 175 196 1-Azatricyclo- [7,4,0,0.sup.2,6 ]- tridecane ##STR205## 165- 176 197 1-Azatricyclo- [7,4,0,0.sup.3,7 ] tridecane ##STR206## 164- 174 198 1-Azatricyclo- [7,4,0,0.sup.3,8 ]- tridecane ##STR207## 165- 175 199 4-Azatricyclo- [8,3,0,0.sup.4,9 ]- tridecane ##STR208## 166- 176 200 2-Azatricyclo- [8,3,0,0.sup.2,8 ]- tridecane ##STR209## 165- 175 201 3-Azatricyclo- [8,3,0,0.sup.3,9 ]- tridecane ##STR210## 165- 175______________________________________

Claims

1. A perfluoro compound represented by the formula, ##STR211## wherein k, j, l and m are zero or an integer of from 1 to 3, and n is an integer of from 1 to 3, the rings A, B and C being optionally substituted with at least one trifluoromethyl group.

2. A perfluoro compound of claim 1, of which formula is ##STR212## wherein k is an integer of 1 or 2; l, m and n are zero or an integer of 1 or 2, any member of the formula being optionally substituted with at least one trifluoromethyl group.

3. A perfluoro compound of claim 1, of which formula is ##STR213## wherein k and n are an integer of 1, 2 or 3; l and m are zero or an integer of 1, 2 or 3, any member of the formula being optionally substituted with at least one trifluoromethyl group.

4. A perfluoro compound of claim 1, of which formula is ##STR214## wherein k and j are zero or an integer of 1, l, m and n are zero or an integer of 1 or 2, any member of the formula being optionally substituted with at least one trifluoromethyl group.

5. A perfluoro compound of claim 1, of which formula is ##STR215## wherein l and m are zero or an integer of 1, 2 or 3; n is an integer of 1, 2 or 3, any member of the formula being optionally substituted with at least one trifluoromethyl group.

6. A perfluoro compound of claim 1 which has 9 to 12 carbon atoms.

7. A composition for use as a blood substitute or infusion fluid which composition is an aqueous emulsion of a perfluoro compound as defined in claim 1.

8. A composition according to claim 7, which contains from 5 to 50% (w/v) of the perfluoro compound as defined in claim 1, and as emulsifier, a nonionic surfactant and/or phospholipid.