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    • 专利摘要:

    公开号:SU944498A3
    申请号:SU792723298
    申请日:1979-02-14
    公开日:1982-07-15
    发明作者:Самэн Даниель；Декуэн Шарль；Кюнеш Жерар
    申请人:Де Ля Решерш Агрономик (Фирма)；
    IPC主号:
    专利说明:

    (5) METHOD FOR OBTAINING TRANS-TRANS-DIEN ALCOHOLS
    I SERIES
    -to-OMtsf
    HCG

    ldBgSn -... sn;, o-XP-f
    CHjBr
    -oo
    moyij D / sulfonic / 01P {c + OAZOL
    39 1984
    The yield of the target product, considering the closest to the proposed derivative 3, is 2% in% l. is the ways carried out
    ..j, ™, / he.o
    CHf
    rtti / J
    , 1Ш;
    in
    CHiOH 5 BrCH2., OH BrCH, x,., CH, CH.EHGHT with EC / Trans-Tan trans-Cis trans-HUI G j fT-mol / 0) (po tuclo / ng 0 ethanol The disadvantage of the well-known: is that the desired product is obtained with a yield of "7.5 as a mixture of trans-trans-79, U, trans trans 8,7 and other isomers 12.2% isomers. Thus, the known method does not have sufficient stereo selectivity and requires subsequent purification, which affects the final yield of the target product. The aim of the invention is to increase the yield and purity of the target product. then according to the method of obtaining trans trans-diene alcohols of the aliphatic series of the general formula - c - "- | mon., .- ™" where R is a normal alkyl n - an integer of 1-5, by the interaction of an organomagnesium derivative of the general formula XMg- (CHi ) ,, where X is HLOR7 bromine;
    according to the scheme:
    f8%
    about mdVgSNg
    .CHOORO-nJ Cr-n --- sn С%: P is a suitable group selected from tetrahydropyranyl or tetrahydrofuranyl radical, with a diene compound in the medium — tetrahydrofuran at O – C –YC in the presence of a catalyst of a mixture of copper chloride and lithium or dilithium tetrachlorocuprate, followed by hydrolysis in the presence of an aromatic sulfonic acid; as a diene compound, use is made of the trans-trans configuration of the general formula KH. li where R and R have the indicated meanings. It is preferable to use an organomagnesium derivative in an excess of 0,, 6 mol per 1 mol of diene compound.; The proposed method allows to obtain the desired product with 99.5 purity and a yield of 60-b2. The catalyst is used in an amount of 0.0 mol per 1 mol of the derivative of formula (1I). Example 1. Preparation of acetoxy-1-hexadiene-2E, 1E:. IlO (formula (Ml), R, i -COCH, 1 kg hexadiene-2E, E-ol-1 (stereo chemical purity 98 E, E7 is dissolved in 2.8 l of pyridine (previously distilled over caustic potassium)). The solution is cooled to a temperature below 10 ° C and 2.8 liters of acetic anhydride are added over 2 hours. After the addition is completed, the temperature is left to rise for 3 hours. Then the reaction mixture is poured onto 10 kg of crushed ice and extracted twice l technical pentane. The organic phase is successively washed with water (500 cm), 2 N. sulfuric acid (500 cm), a saturated solution of bicarbonate on (500 cm), again with water and finally with a saturated solution of sodium chloride (500 cm), After drying over magnesium sulphate, distilling off pentane and distilling the resulting residue, 1, 638 kg of acetate (81) were distilled; mp 78 ° C / 20 mm Hg Using the same procedure, the results are obtained from heptadiene-2E, E-ola-1, acetoxy-1-heptadiene-E, (E; yield 80%, bp mm hg. Example. Preparation of (chloro-6-hexyloxy) -2-tetrahydropyran: 220.5. Kg of technical chloro-6-hexanol-1 is poured into a 10-liter reactor and 7.5 cm of concentrated hydrochloric acid is added. The reaction mixture is cooled to a temperature below + 10 ° C with brine (crushed ice + methanol and 2,125 kg of freshly distilled dihydropyran are added over 3 hours in 100 cm portions of 100 cm. After the addition is left, it is left at 3 at ambient temperature, diluted 2 liters of ether and the reaction mixture is washed successively with 500 ml of 2N sodium hydroxide, 2 liters of water and 2 liters of a saturated solution of sodium chloride, dried over magnesium sulfate, the ether is distilled off and the residue is distilled in vacuo. O-lSO C / OI mm Hg main fraction, co corresponding to the target product, U, 311 kg (9U output, mp 10b – 110 C / 0.1 mmHg. The product has the following IR spectrum IR (film ;; strip 2930, 2860, 6Q,, 1350, 1200 , IZO, 1120, 1075, 1030, 900, 865, 810 cm. Example 3. Preparation of dodecadien-8E, 10E-ola-1 tetrahydropyranyl ether: Formula TV, 1 5 and P-tetrahydropyranyl) Reactions were carried out in an argon atmosphere. Preparation of organomagnesium compound (chloro-6-hexyloxy -2-tetrahydropyran. Into a tank reactor equipped with a mechanical stirrer, a dropping funnel and a reflux condenser, 60 g of magnesium chips are introduced and 100 ml of tetrahydrofuran (THF) are poured over it. 10 g (chloro-b-hexyloxy) -2-tetrahydropyran is immediately added. according to the method described in example 2, And heat the reaction mixture under reflux. As soon as boiling begins, 5 cm of dibromoethane is added, a very rough reaction occurs with the participation of magnesium and blackening of the reaction mixture. The stirrer is switched on and, while continuously maintaining the effect of the reflux condenser, a solution of k2S g (chloro-b-hexyloxy -2-tetrahydropyran in 1, 5 l THF) is introduced dropwise in 2 hours. After the addition is completed, the mixture is allowed to heat under reflux 3 hours and then left overnight at ambient temperature. Acetoxy-1-hexadiene-2E combination obtained in Example 1 with an organomagnesium compound. A solution of 180 is siphoned into a 6 liter reactor equipped with a mechanical stirrer and a thermometer. g acetoxy-1-hexadiene-2 E, E in 1.5 l of THF. The reaction mixture is cooled before and (si ((young) solution of 4.3 g of anhydrous lithium chloride and 6.8 g of anhydrous copper chloride (1 in 90 cm THF is added. The reaction mixture stains in red-orange color. Then a solution of the organomagnesium compound is added for about 1 to 5 hours, without giving the temperature a rise. At the beginning of the addition, the reaction mixture is colored light green, then almost completely discolored and finally colored black-violet Colour. After the addition is complete, the reaction mixture is left for 3 hours at 0 ° C, cooled again before and hydrolyzed with a saturated solution of ammonium chloride with vigorous stirring until the solution becomes colorless and the precipitate is deposited on the bottom of a rich black and viscous precipitate. The supernatants are decanted and the residue is triturated three times with 200 cm portions of ether. The organic phases are combined and washed successively with an overhead ammonium chloride solution (500 cm 2 times then with a saturated solution of sodium chloride (500 cm 2 times. The organic phases are transferred directly to an evaporator. After distilling off the solvent under rarefaction (50 mm, the residue is obtained) mainly from dodecadien-8E, 10E-ol-1 tetrahydropyranyl ether, Example: Preparation of dodecadien-8E, 10E-ola-1 ({formula (T), 5, The residue obtained in Example 3 is dissolved in 2, 5 liters of methanol and 250 cm of water are added, and g of N-toluenesulfonic acid is added. The mixture is distilled at 3 hours and left overnight at ambient temperature. finally with a saturated solution of sodium chloride. Then dried over magnesium sulphate. After distilling off the solvent by distillation of the residue (270 g), 59 g of the head product are obtained, b.p. 0-98C / 0.1 mmHg, g dodecadien-8E, 10E-ola-1, bp.98100C / 0, .1 mmHg, crystallizing during the distillation process, and 71 g of residue consisting mainly of dodecanediol. The yield of dodecanediene-8E, 1OE-ola-1 after distillation and crystallization of 62.5 sec per Used acetoxy-1-hexadiene-2E, tE. The stereochemical purity of the product (determined by gas chromatography: 5 m column of stainless steel. 1/8 3 FFAP (chromium SNR. 80/100190 C) is characterized by the following parameters: IR spectrum (); bands 3370 (OH associated); 1615 (); 1055 (primary OH); 980 (,, Е, conjugated). The absence of the band 950 ct indicates the absence of the isomer 82.10 E. The NMR spectrum (sG, MD, 250 MHz, CDCH, 1,3, c, extended 8Н, iCHz .; 1 ,, quintet, .2Н, -СН. in С; 7, f, ЗН, -CHj; 2, Oif, apt., 2Н- 3.6, t., ЛИ, - CH-2.0H; 5.5, M., 2H, H and -; 5.96, 2H, H9 and H o - Mass spectrum of M 182; fragments, 0); 135 C (4.0 + 121, 107, 81, 79, 68, 67, 55,, 32. The melting point is 29-30 ° C. According to one of the Before the method of vacuum distillation, the dodecanediol can be separated from the crude hydrolysis product by a method of dissolving pentane in a triplicate and then left at ambient temperature by 3. Under these conditions, the dodvinciol precipitates and can be removed by drying in a vacuum. dodeca..diene-8E, 1OE-ola-1 (formula (l), R CH, I 5. Under the conditions described in examples 3 and, the synthesis of 1,100 kg of dodecadien-8E, 10E-ol-1 was carried out, based on the following amounts of solvents and reagents: (Chloro-6-hexyloxy) -2-tetrahydropyran, Magnesium, g Acetoxy-1 -hexadiene-2E ,, kg Anhydrous lithium chloride, g Anhydrous copper chloride (1). g THF, l Methanol, l p-Toluenesulfonic acid, g The yield of distilled and recrystallized dodekadien-8E, Eu-ola-1 60. Dodecadien-8E, 10E-OL-1 can be obtained analytically pure by the following method. 1fOg of dodecadien-8E, 1 OE-ol-1, obtained according to the described reaction, is dissolved in 280 cm of pentane (grade Bike-Malicort nanograd, nanograde Byke Malllncrot). The solution is slowly cooled to -10 ° C, during which time dodecadien-8E crystallizes as white needles. They are pressed at -10 ° C and get 133 g of dodekadien-8E, Eu-ola-1, a high degree of purity of which is confirmed by the results of gas chromatography of the ik graph (under the described conditions). Melting point Example $. Preparation of acetoxy-1-octadiene-2E, 4E, formula (III), LH and N COCHj). First, technical octadien-2E5 E-ol-1 is recrystallized from pentane in the cold. 10 g (0.08 mol) of recrystallized alcohol is acetylated using 16.3 g (0.16 mol) of acetic anhydride in pacTBdpe 20 ml of pyridine. After a three-hour aging at ambient temperature, the product is hydrolyzed in the usual way and 12 g (90) of the corresponding acetate are obtained, b.p., 50 ° g / 0.1 mm Hg. Gas chromatography: single product on a column of 5% E.C..N.S.S.M. chromium gas (Gas chrom () 100: 120 mesh, 3 m stainless. 1/8, film: 17 "0i IR spectrum (cm (ester)), -C C-1b60, conjugate 99P (s) and ( W). Example 7. Preparation of dodecadien-BE, 8E-ol-1, formula (t), n 3 and its acetylated derivative. To the acetate obtained. In Example 6 (ti g, 0.023 mol ;, added in the presence of 8 ml of the solution of methyl tetrachlorocuprate prepared by the described method at -10 ° C is an excess of organomagnesium compound (chlorine-C-butyloxy -2-tetrahydropyran (35 cm of a 1N solution in TGO under the same reaction conditions described above in Example 3), After hydro The solvent is distilled off and the residue is distilled off. The residue is treated with l-toluenesulfonic acid in methanol under the same conditions as described in the example, resulting in dodecadien-BE, 8E-ol-1. It is treated in crude form with acetic anhydride (3.36 g , 0.033 mol, in the usual way, 3.3 g {6k%) of acetoxy-1-dodekadien-BE, 8E are obtained; bp 88 C / 0.1 mmHg Gas chromatography: the only product on column 3 FFAP , gas chrome (Gas Chrom G) 5 m stainless. 1/8, IR spectrum: (cm, film) (ester), 985 (s) and 955 (W) E are conjugate. Example 8. Preparation of acetoxy-1-nonadiene 2E, 4E formula (CBI), R C4.H9 and. First total technical nonadiene-2E, E-ol-recrystallized from pentane. 10 g (0.071 mol of alcohol are acetylated using 1, g (0, zero} of acetic anhydride in a solution of 20 ml of pyridine. After usual treatment, 11.5 g (87%) of acetate are obtained, boil. 70 ° C / 0.1 mm Hg gas chromatography: single product, 5 ECNSSH per chromium gas (Gas Chrom G) 100/120 mesh, 3 m. stainless, 1/8,, IR spectrum (film, cm), (ester); 1660 (); 950 (c) and (W) (, E is matched to Example 9. Preparation of tetradecadien-7E, 9E-ol-1 (formula (1), and n -k) and its acetylated derivative. To the acetate obtained in the example 8 (5 g, 0.027 mol) was added in the presence of 10 ml of a solution of dilithi tetrachlorocuprate, at -10 ° C, 5 cm of a 1N solution of an organomagnesium compound {chlorine-5-.netiloxy -2-tetrahydropyran in THF under the same conditions as described in example 3. After hydrolysis and distillation, the solvent residue is treated with toluene and sulfonic acid in methanol under the same conditions as in example k, and get tetradekadien-7E, 9E-o -1. The latter in the crude form of treatment ". "", "" Are melted with acetic anhydride (3.6 g, 0.036 mol) in the usual way and half a gram of k g (60%) of acetoxy-tetradecadien-7E, 9E is obtained, b.p. 105C / 0.1 mmHg Gas chromatography: single product, 3 F.F.A.P. gas chrome (Gas chrom G) 5 m stainless. 1/8, IR spectrum (film, cm;: (ester);, E, conjugated: 935 (s) and 955 (W), claims 1. Method for the preparation of trans-trans alcohols of aliphatic ratios of formula. / CH ,. (CH,) where R is the normal structure of the vaquyl n is an integer by the interaction of the organomagnesium derivative of the general formula: JCKg-cCH in-CH op, where X is chlorine, bromine, P is a protective group, selected from the tetrahydropyranyl or tetrahydrofuranyl radical, with the diene compound Nium in tetrahydrofuran medium at BUT) -0 ° C about the presence of a mixture of copper chloride and lithium or dilithium tetrachlorocuprate with the following by hydrolysis in the presence of an aromatic sulfonic acid, characterized in that, in order to increase the yield and increase the purity of the target product, trans acetate configuration of the general formula is used as the diene compound 2, where Gg 4 - has the specified value; -acetyl group. 2, the method according to claim 1, in which the organic magnesium derivative is used in an excess of 0.25-0.6 mol per diene compound. Sources of information, taken into account in the examination 1.De K. Can Synthesis de La coldemone Tetrahedron, 30,, p. 3807-3810. 2. US patent number 3825607, cl. 260-65, published, 1975.
    权利要求:
    Claims (2)
    [1]
    Claim
    1. The method of obtaining trans-transdiene alcohols of the aliphatic series of the General formula
    P / G (CH,) ' CH " 0H ' l II n H π
    944498 12 where R is the normal structure of alkyl C f “C 4 ;
    η is an integer of 1-5, by the interaction of an organomagnesium derivative of the general formula:
    hmd- (sn g ) p -sn g op, where X is chlorine, bromine, '
    P is a protective group selected from tetrahydropyranyl or tetrahydrofuranylradical with a diene compound of Ni in tetrahydrofuran medium at (• 10) -O ° C in the presence of a mixture of copper chloride and lithium or dilithium tetrachlorocuprate followed by hydrolysis in the presence of aromatic sulfonic acid, characterized in that, in order to increase the yield and purity of the target product, 'as a diene compound
    Trans-trans acetate acetate of the general formula is used:
    H N 5 l
    And n where R - has the indicated value;
    Rj is an acetyl group.
    10 2. The method according to p. ^ Characterized in that the organomagnesium derivative is used in excess of 0.25 “0.6 mol per 1 mol of the diene compound.
    15 Sources of information, taken into account in the examination
    1. De K. Mogu Synthesis de La coldemone Tetrahedron, 30, 1974, p. 3807-3810.
    [2]
    2ό 2. US Patent Ν ’3825607, CL 260-654, published. 1975.
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    AT370404B|1983-03-25|
    CA1121832A|1982-04-13|
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    FR7804257A|FR2417487B1|1978-02-15|1978-02-15|
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