NEW COMPOSE ORGANIC NITROGEN USABLE LIKE PRECURSORS OF CATALYTIC COMPOSITION.

The present invention relates to novel nitrogen-containing organic compounds with applications as a ligand transition metal. The compounds may be used for the catalysis in particular for the dimerization, codimerisaion, oligomerization or polymerization of olefins.

The a-linear olefins, especially those containing 4 to 20 carbon atoms, having outlets varied according to the length of their carbon chain. For example, the C4 to C8 olefins are used primarily as comonomers for the manufacture of low density polyethylenes (LLDPE), the C8 to C14 as intermediates in the industry and the lubricants C8-C18 for the detergent. The olefins know a high economic growth. Most of the industrial processes for the production of a-olefins are methods of oligomerization of ethylene catalyzed by transition metal complexes.

The thus assists for several years to a search to find new ligands incessant in the field of catalysis homogeneous systems that may lead to more selective, optionally more active and recyclable, and this in particular for the polymerization or oligomerization of ethylene. The nitrogen ligands bis-imino-pyridines or imino-pyridines have received particular interest, in particular for their steric and electronic and scalable for their coordination so as bidentate or tridentate on the transition metals. The article published recently (Chem. Rev. 2007, 107, 1745-1776) present the last developments made around this family of ligands.

Surprisingly, we have discovered novel nitrogen-containing organic compounds that can be used in the field of homogeneous catalysis.

The present invention relates to novel nitrogen-containing organic compounds with high potential for applications by homogeneous catalysis, obtained by reacting a compound X of substituted pyridine type with a compound Y amino-quinoline.

Disclosed is the organic nitrogen compound A usable as ligand by homogeneous catalysis having the following general formula:

wherein R2 to R-10, same or different, are selected from hydrogen, alkyl groups, saturated or unsaturated, cycloalkyl or aromatic, aryl or alkaryl, optionally substituted, alkoxy groups, aryloxy or amino, a halide.

In the compound A, the groups R2 to R₁₀ , same or different, may also be organic radicals in which one or more hydrogen atoms are replaced by halides, for example a fluoride, or groups containing at least one heteroatom such as oxygen, nitrogen, sulfur, phosphorus or silicon. These heteroelements may be included in cycles saturated or unsaturated alkyl or aromatic.

Disclosed is the organic nitrogen compound usable as ligand B by homogeneous catalysis having the following general formula:

wherein Ri to Ru, same or different, are selected from hydrogen, alkyl groups, saturated or unsaturated, cycloalkyl or aromatic, aryl or alkaryl, optionally substituted, alkoxy groups, aryloxy or amino, a halide, Ri is different from the methyl radical.

In the compound B, the groups Ri to Ru, same or different, may also be organic radicals in which one or more hydrogen atoms are replaced by halides, for example a fluoride, or groups containing at least one heteroatom such as oxygen, nitrogen, sulfur, phosphorus or silicon. These heteroelements may be included in cycles saturated or unsaturated alkyl or aromatic.

The present invention also provides the method of manufacturing products A B and comprising at least one step which consists in reacting, preferably in a solvent, a compound X belonging to the family of substituted pyridines having at least one ketone functional group, with a compound Y belonging to the family of aminoquinolines and derivatives thereof.

The method of the present invention may also comprise at least one additional step for performing a substitution reaction groups.

The compound X has the following general formula:

The compound Y belongs to the family of aminoquinolines and derivatives thereof. Corresponding The general formula is written below:

with Ri to Rii, same or different, are selected from hydrogen, alkyl groups, saturated or unsaturated, cycloalkyl or aromatic, aryl or alkaryl, optionally substituted, alkoxy groups, aryloxy or amino, or halides, Ri is different from hydrogen.

The compound X is, for example, 2-acetylpyridine, 4-methyl-2-acetylpyridine, 2-bromo-6-acetylpyridine, 6-methyl-2-acetylpyridine, 2-methoxy-6-acetylpyridine.

The compound Y is, for example, 8-aminoquinoline, or 2-methyl-8-aminoquinoline.

The reaction between the two compounds X and Y is preferably carried out in a solvent, at a temperature of preferably between 20 and 250 °C. The compounds X and Y can be introduced in any order.

The solvents used are selected from standard organic solvents polar or apolar, aprotic or practices, such as aliphatic or aromatic hydrocarbons such as toluene, xylene, cyclohexane, chlorinated solvents such as dichorométhane , the nitro solvents such as acetonitrile, alcohols such as methanol or ethanol. These solvents can be used alone or as a mixture. The solvents are preferably dried, by distillation or by passage over an adsorbent, before being used.

The reaction of X with Y is preferably performed in the presence of a catalyst. The catalysts are preferably selected from Bronsted acids or Lewis acids.

Bronsted acids are H⁺ X ' in which X is an anion. The anions X^- are preferably selected from among the anions of tetrafluoroborate, tétraalkylborates , hexafluorophosphates, hexafluoroantimonates , alkyl sulfonates (for example the methylsulfonate), p-toluenesulfonates, perfluorosulfonates (for example the trifluoromethylsulfonate), fluorosulphonates, sulfates, phosphates, perfluoroacétates (for example the trifluoroacetate), perfluorosulphonamides (e.g. amide bis-trifluoromethanesulfonyl of formula N (CF3SC > 2) 2'). fluorosulphonamides, perfluorosulfométhides (for example the methide tris-trifluoromethanesulfonyl of formula C (CF3S02) 3"). carboranes, tetraphenylborates and tetraphenylborate anions wherein the aromatic rings are substituted.

Lewis acids are by definition compounds that can accept a lone pair of electrons.

For example, include lanthanide triflates, in particular the ytterbium triflate (Yb (OTf)₃ ), the scandium triflate.

The reaction between X and Y may optionally be performed in the presence of iodine.

The reaction between the compounds X and Y releases water. The water may be advantageously trapped during the reaction by adding a desiccant such as molecular sieve. It can also be removed by azeotropic distillation with the solvent of the reaction.

The molar ratio of the compound X and Y the compound is between 0.1 and 10, preferably between 0.2 and 5.

The main product obtained in the reaction of X with Y may be isolated and purified according to the methods conventional in organic chemistry such as precipitation, crystallization or separation by liquid chromatography on a column of alumina and silica.

The following examples illustrate the invention without limiting its scope.

The condensation of 6.89 g of 2-acetylpyridine (56.9 mmol) and 4.1 g of 8-aminoquinoline (28.4 mmol), with 1.3 ml of formic acid HCOOH is carried out in 75 ml of anhydrous MeOH. The reaction medium is stirred at reflux for 72:00. After evaporation methanol under vacuum, the ketone is evaporated by pulling vacuum and heating to 60 °C. The obtained crude product was purified by column chromatography on alumina to remove the 8-amino quinoline, and then on neutral silica (eluent CH₂ Cl2/ AcOEt 80/20). 2,4 g of a yellowish solid are obtained. The yield obtained is 30%.

The characterisations are made by methods for NMR analysis of the¹ And the H¹³ C, by IR spectroscopy by mass spectroscopy and GC/MS.

NMR¹ H: Ôh (300 MHz, CD₂ THIS₂ ) 1.90 (s, 3:00), 6.17 (d, 1:00, J 2.3 Hz), 6.95 (d, 1:00, J 8.6 Hz), 7.00 (s, 1:00), 7.11 (ddd, 1 H, J 7.3, and 1.4 4.7 Hz), 7.29 (ddd, 1 H, J 7.6, and 1.2 4.7 Hz), 7.32 (d, 1 H, J 8.5 Hz), 7.35 (dd, 1 H, J 8.2 and 4 . 35:00 z), 7.49 (dt, 1 H, J 7.9 and 1.1 Hz), 7.59 (dt, 1 H, J 7.94 1 and. 15:00 z), 7.62 (td, 1 H, and 1.9 J 7.5 Hz), 7.76 (td, 1:00, J 7.65 and 1, 2:00 z), 8.02 (dd, 1 H, J 8.3 and 1.8 Hz), 8.60 (dq, 1 H, J 4.8 and 0.9 Hz), 8.69 (dq, 1 H, J 4.9 and 0.9 Hz), 8.75 (dd, 1 H, J 4.2 and 1.7 Hz) PPM;

NMR¹³ C: δ ℮ (75MHz, CD₂ THIS₂ ) 31,1, 59,1, 113,8, 115,5, 120,3, 121,8, 121,9, 122,7, 123,9, 125,1, 128,9, 130,0, 136,1, 136,5, 136,8, 136,9, 137,7, 140,6, 148,0, 149,61, 149,64.158,2, 166,6 pPM;

IR: 3371, 3048, 2968, 1632, 1583, 1563, 1508, 1464, 1428, 1378, 1294, 1225, 1100, 1044, 991.823, 804, 783, 750 cm'¹ .

GC/MS: 350, 335, 272, 256, 167.

The A structural formula of the product obtained is as follows:

The synthesis is carried out as in the Example 1, except that is used 4.00 g of 4-methyl-2-acetylpyridine (29.6 mmol) and 4.27 g of 8-aminoquinoline (29.6 mmol).

This mixture is placed in solution in 60 ml of MeOH with 0.8 ml distilled formic acid and then heated at reflux for 96 hours.

1,8 bright yellow g of a solid are obtained, which corresponds to a yield of 32%.

The solid is characterized by NMR¹ H,¹³ C, IR and by mass spectroscopy.

NMR¹ H:5_h (300 MHz, CD₂ THIS₂ ) 1.85 (s, 3:00), 2.28 (s, 3:00), 2.40 (s, 3:00), 6.10 (d, 1:00, J 2.3 Hz), 6.93 (d, 1:00, J 8.6 Hz), 6.96 (m, 1:00), 7.12 (dm, 1:00, J 5. 0:00 z), 7.30-7.40 (m, 4:00), 8.01 (dd, 1:00, J 8.4 hz and 1.4), 8.44 (d, 1:00, J 4.9 Hz), 8.52 (d, 1:00, J 5.1 Hz), 8.74 (dd, 1 H, and 1.7 J 4.2 Hz) PPM;

NMR¹³ C:TO_c (75MHz, CD₂ THIS₂ ) 21,2, 21,4, 31,2, 59,1, 113,7, 115,4, 121,2, 121,8, 122,9, 123,7, 124,7, 125,3, 128,9, 129,6, 136,1, 136,4, 137,8, 140,6, 147,9, 148,1, 148,2, 149,31, 149,32.158,2, 166,4 pPM;

IR: 3359, 2974, 2921, 2822, 1640, 1599, 1555, 1509, 1467, 1448, 1423, 1378, 1350, 1116, 1090, 1031.991.847, 827, 803, 779, 711.696 cm'¹ .

MS:El m/z 363, 286, 270, 256, 243, 189, 181.

The A structural formula of the product obtained is as follows:

compound X

The reaction of 2-bromo-6- acétvlpvridine with the 8-aminoquinoline:

0,5 g of 2-bromo-6- acetylpyridine (2.5 mmol), 0,36g of 8-aminoquinoline (2.5 mmol) are dissolved in 4.25 ml of freshly distilled methanol. 0,05 ml of HCOOH are added and the reaction medium is brought to reflux for 4 days. The precipitate is filtered and washed been found at cold MeOH then dried in vacuum. 0,35g (0.68 mmol) of pure yellow solid are obtained, which corresponds to a yield of 54%.

NMR¹ H: Ôh (300 MHz, CD₂ THIS₂ ) 1.89 (s, 3:00), 6.13 (d, 1:00, J 2.3 Hz), 6.87 (s, 1:00), 7.00 (s, 1 H, J 8.7 Hz), 7.27-7.33 (m, 2:00), 7.39 (dd, 1 H, J 8.4 and 4.2 Hz), 7.43-7.54 (m, 4:00), 7.63 (t, 1 H, J 7. 7:00 z), 8.05 (dd, 1 H, J 8.3 and 1.7 Hz), 8.76 (dd, 1 H, J 4.2 and 1.7 Hz) PPM;

NMR¹³ C: δ ℮ (75MHz, CD₂ THIS₂ ) 30,5, 59,1, 114,5, 114,8, 119,5, 122,1, 122,9, 124,6 126,4, 127,2, 129,4, 130,2, 135,5, 136,2, 137,7, 139,4, 139,6, 140,3, 141,8, 142,2 148,2, 159,0.168,1 pPM;

The A structural formula of the product obtained is as follows:

The condensation of 1.95 g of 6-methyl-2-acetyl-pyridine (14.4 mmol) and 2.08 g of 8-aminoquinoline (14.4 mmol), 0.4 ml HCOOH with formic acid is carried out in 30 ml of anhydrous MeOH. The reaction medium is stirred at reflux for 96 h. After evaporation methanol under vacuum, the crude product is purified on a silica column (eluent: CH2Cl2/ethyl acetate 95/5). 0,8 g of a bright yellow solid are obtained (yield 17%).

NMR¹ H:5_h (300 MHz, CD₂ THIS₂ ) 1.87 (s, 3:00), 2.54 (s, 3:00), 2.59 (s, 3:00), 6.12 (d, 1:00, J 2.3 Hz), 6.93 (d, H, J 8.7 Hz), 6.94 (s, 1:00), 6.97 (dt, 1 H, J 7.5 and 0 . 75:00 z), 7.15 (dm, 1:00, J 7. 7:00 z), 7.27 (dm, 1:00, J 7 . 3:00 z), 7.29-7.38 (m, 3:00), 7.50 (t, 1:00, J 7.7 Hz), 7.64 (t, 1 H, J 7.7 Hz), 8.01 (dd, 1 H, and 1.7 J 8.2 Hz), 8.75 (dd, 1 H, J 4.2 and 1.8 Hz) PPM;

NMR¹³ C: δ ℮ (75MHz, CD₂ THIS₂ ) 24,69, 24,72, 31,1, 59,1, 113,7, 115,6, 117,1, 120,9, 121,4, 121,7, 122,1, 125,3, 128,9, 129,9, 136,1, 136,3, 137,1, 137,7, 140,6, 147,9, 157,7, 158,36, 158,49, 165,9 pPM;

The A structural formula of the product obtained is as follows:

The synthesis of 2- methoxv -6- acétvlpvridine :

The reaction of 2- methoxv -6- acétvlpyridine with the 8-aminoquinoline:

0,5 g of 2-methoxy-6- acetylpyridine (3.3 mmol), 0,47g of 8-aminoquinoline (3.3 mmol) are dissolved in 5.6 ml of freshly distilled methanol. 0,07 ml of HCOOH are added and the reaction medium is brought to reflux for 4 days then evaporated under vacuum. The brown oil obtained is purified by flash column chromatography on silica (eluent: CH2Cl2 100% and CH₂ Cl2/ AcOEt , 80/20). A pure solid is obtained. NMR¹ H: Ôh (300 MHz, CD₂ THIS₂ ) 1.88 (s, 3:00), 3.92 (s, 3:00), 3.93 (s, 3:00), 6.23 (d, 1:00, J 2.3 Hz), 6.52 (dd, 1:00, J 8.3 and 0.6 Hz), 6.74 (dd, 1:00, and 0.6 8.2 Hz), 6.95 (d, 1 H, J 8.6 Hz), 7.07 (m, 3:00), 7.35 (dd, 1 H, J 7.4 and 4.3 Hz), 7.41-7.51 (m, 2:00), 7.66 (dd, 1 H, and 7.3 J 8.3 Hz), 8.01 (dd, 1 H, J 8.3 and 1.6 Hz), 8.73 (dd, 1 H, J 4.2 and 1.7 Hz) PPM;

NMR¹³ C: δ ℮ (75MHz, CD₂ THIS₂ ) 31,0, 53,5, 53,6, 58,6, 108,8, 109,8, 112,5, 113,9 (2C), 116,5, 121,2, 125,4, 128,8, 129,9, 136,0, 136,2, 139,3, 139,5 (2C), 141,0, 147,9, 155,9, 163,8, 164,0, 164,6 PPM.

IR: 3384, 2972, 2945, 1630, 1575, 1477, 1461, 1430, 1254, 1053, 797 cm'¹ .

SM:El m/z: 410, 395, 302, 286, 258.

The structural formula of the product obtained A is as follows

1,5 g (2.94 mmol) of product A obtained according to the Example 3 and 0.21 g (0.18 mmol) of tétrakispalladium (0) are dissolved in 12 ml of toluene. A degassed solution of 1.25 g (11.8 mmol) of Na₂ C03 in 6 ml of distilled water and 0.86 g (7.0 mmol) phenyl boronic acid are added. The reaction medium is brought to reflux for 24:00. Then 4.5 ml of an aqueous solution at 20% of NH₃ diluted in 30 ml of a saturated aqueous solution of Na₂ C0₃ are added. The aqueous phase is extracted with CH₂ THIS₂ (3x50mL), the joined organic phases are washed with brine, dried on MgSC > 4, filtered then evaporated under vacuum. The crude product is purified by flash column chromatography (eluent: CH₂ THIS₂ 100%). m 1.56 g. High yield: 44%.

NMR¹ H: Ôh (300 MHz, CD₂ THIS₂ ) 2.01 (s, 3:00), 6.37 (d, 1:00, J 2. 2:00 z), 6.99 (d, 1:00, J 8.6 Ηζ), 7.22 (bs, 1Η), 7.36-7.60 (m, 11:00), 7.69-7.85 (m, 3:00), 8.02-8.12 (m, 5:00), 8.8 (dd, 1 H, J 4.2 and 1 . 5:00 z);

NMR¹³ C: δ ℮ (75MHz, CD₂ THIS₂ ) 31,3, 59,3, 114,0, 115,9, 118,4, 118,8, 119,2, 121,8, 122,4, 125,4, 127,3, 128,9, 128,9, 129,0, 129,2, 129,3, 130,3, 136,1, 136,7, 137,8, 137,9, 139,7, 141,2, 148,0, 156,5, 156,7, 158,1, 166,5 pPM.

IR: 3360, 3058, 2964, 1633, 1587, 1564, 1508, 1468, 1441, 1379, 1260, 1158, 1092, 1061, 1026, 989, 814, 800, 760, 692, 659 cm'¹ .

SM:El m/z\ 502, 487.348, 243.

The A structural formula of the product obtained is as follows:

Charbonnière. L. S. Synthesis 2006.18. 3128-3133 :

room temperature, the reaction medium is neutralized with 150 ml of a saturated aqueous solution of NaHC0₃ . The aqueous phase is extracted with AcOEt (3x50 ml). The joined organic phases are washed with a saturated aqueous solution of Na₂ S₂ 0₃ (2x50 ml) followed by brine (2x50 ml). MgS04 The organic phases are dried, filtered and vacuum evaporated. The crude product is purified by flash column chromatography on silica (eluent:

CH₂ THIS₂ 100%). 1,251 g of beige solid are obtained. High yield: 89%.

δπ (300 MHz, CD2CI2) 2.69 (s, 3:00), 4.96 (bs, 2:00, NH₂ ), 6.88 (dd, 1:00, J 7.4 and 1.3 Hz), 7.09 (dd, 1 H, and 1.3 J 8.1 Hz), 7.25 (m, 2:00), 7.96 (d, 1 H, J 8.4 Hz); NMR¹³ C:

δ ℮ (75MHz, CD2CI2) 25,0, 109,8, 115,6, 122,2, 126,4, 127,0, 136,0, 137,8, 143,7, 156,3 PPM;

IR: 3467, 3385, 3343, 2365, 3048, 2917, 1616, 1595, 1563, 1507, 1475, 1431, 1373, 1344, 1323, 1284, 1274, 1243, 1137, 1080, 1032, 828, 794, 744, 715, 692 cm'¹ .

SM:El m/z: 158, 131, 103.

The reaction of 2- acétvlpyridine with the 2- méthvl -8-aminoquinoline:

1 g of 2-methyl-8-aminoquinoline (6.32 mmol), 1.42 ml of 2-acetylpyridine and several drops of HCOOH are dissolved in 10 ml of freshly distilled MeOH. The reaction mixture is stirred for 5 days at reflux. The reaction medium is then evaporated under vacuum. The crude product is then purified by flash column chromatography on silica (eluent: CH2CI₂ / AcOEt , 90/10 AcOEt and 100%). 0,823 mg of a brown yellow solid are obtained, or a yield of 43%.

NMR¹ H: Ôh (300 MHz, CD₂ THIS₂ ) 1.89 (s, 3:00), 2.72 (s, 3:00), 6.12 (d, 1:00, J 2.3 Hz), 6.89 (d, 1 H, J 9.3 Hz), 6.93 (bs, 1:00), 7.12 (ddd, 1 H, J 7.2, 4.7 and 1.5 Hz), 7.23 (t, 2:00, J 7.2 Hz), 7.28 (ddd, 1:00, J 7.6, and 1.2 4.8 Hz), 7.47 (dt, 1:00, J 7.8 and 1.1 Hz), 7.56-7.66 (m, 2:00), 8.75 (td, 1:00, J 7.7 and 1.9 Hz), 7.90 (d, 1:00, J 8.4 Hz), 8.60 (ddd, 1:00, J 4.7, and 0.9 1.7 Hz), 8.67 (ddd, 1 H, J 4.9,1.9 and 1.0 Hz) PPM;

NMR¹³ C: δ ℮ (75MHz, CD₂ THIS₂ ) 25,9, 30,8, 59,1, 113,8, 115,5, 120,4, 121,9, 122,6, 122,7, 123,9, 124,1, 136,2, 136,5, 136,8, 136,9, 137,0, 140,0, 149,6 (2C), 156,9, 158,4, 166,8 PPM;

IR: 3373, 3051.2964, 2921, 1633, 1602, 1584, 1564, 1552, 1516, 1646, 1429, 1385, 1369, 1259, 1090, 1044, 1019, 993, 835, 785, 746, 706, 687 cm'¹ .

SM:El m/z: 364, 349.286.

The A structural formula of the product obtained is as follows:

In a balloon surmounted by a Dean-Stark modified to recover solvent which the heavier the reservoir is filled with molecular sieve 3 Â, is 0.85 g (5.2 mmol) of 2, 2-dimethyl-1-pyridin-2-ylpropan-1-one, 1.12 g (7.77 mmol) of 8-aminoquinoline, 15 ml toluene sec and 76 mg (0.4 mmol) of p-toluene sulfonic acid. The reaction mixture is stirred for 3 days at 150 °C. The solvent is then evaporated by pulling vacuum. The 8-aminoquinoline is removed by alumina column chromatography (eluent: CH₂ Cl2/ AcOEt , 80/20). The product crystallizes in the starting ketone. The crystals are washed at n-pentane and drawn vacuum to dry the product. 0,53g almost translucent of a solid are obtained (yield: 35%).

NMR¹ H:TO_H (300 MHz, CD₂ THIS₂ ) 1.41 (s, 9:00), 6.70 (dd, 1 H, J 7.3 and 1.45 Hz), 6.81 (dt, 1 H, J 7.8 and 1 . 15:00 z), 6.93 (ddd, 1 H, J 7.9, 5.0 and 1 . 2:00 z), 7.12-7.24 (m, 2:00), 7.28-7.40 (m, 2:00), 7.27 (dm, 1 H, J 7. 3:00 z), 8.02 (dd, 1 H, J 8.4 hz and 1.74), 8.41 (ddd, 1 H, J 5.0, and 1.2 1.8 Hz) PPM;

NMR¹³ C:5_C (75MHz, CD₂ THIS₂ ) 28,7, 40,7, 118,3, 121,4, 122,4, 122,5, 126,5, 128,9, 135,3, 135,9, 141,4, 148,5, 149,3, 149,6, 157,2, 178,7 pPM;

IR: 3037, 2929, 1644, 15814, 1560.1496, 1477, 1462, 1426, 1391, 1363, 1311, 1251, 1217, 1079, 1056, 1033, 1002, 986, 830, 809, 791, 756, 721 cm'¹ .

GC/MS: 232, 205, 155, 128, 101, 78, 57

The B structural formula of the product obtained is as follows:

In a balloon surmounted by a Dean-Stark modified to recover solvent which the heavier the reservoir is filled with molecular sieve 3Â, is 1.48 g (8.08 mmol) of 2-benzoylpyridine, 1.17 g (8.11 mmol) of 8-aminoquinoline, 25 ml toluene sec and 122.3 mg (0.64 mmol) of p-toluene sulfonic acid. The reaction mixture is stirred for 3 days at 150 °C. The solvent is then evaporated by pulling vacuum. The 8-aminoquinoline is removed by alumina column chromatography (eluent: CH₂ Cl2/ AcOEt , 80/20). The product obtained is solubilized in 30 ml of methanol and 120 ml of n-heptane are added. The solvents are evaporated by azeotropic distillation remove methanol and precipitate the desired product.

1,3 g of yellow solid are obtained (yield: 52%)

IR: 3053, 1641, 1582, 1563, 1494, 1466, 1429, 1379, 1367, 1311, 1244, 1073,

1054,1027, 993, 958, 829, 792, 764, 754, 740, 723, 713, 638, 616, 599, 583 cm'¹ .

GC/MS: 309, 231.205, 181, 154, 128, 101, 77, 51

The B structural formula of the product obtained is as follows: