RU2200146C1 - Method of synthesis of 1,3-dialkyl-2-(n-propyl)-prop-2z-en-1-ols - Google Patents

Abstract

FIELD: organic chemistry, chemical technology. SUBSTANCE: invention relates to method of synthesis of novel 1,3-dialkyl-2-(n-propyl)-prop-2Z-ene-1-ols of the general formula (1):

where R means CH₃, n-C₃H₇; R¹ means n-C₆H₁₃, n-C₈H₁₇. Method involves interaction of terminal allenes of the general formula:

where R¹ is n-C₆H₁₃, n-C₈H₁₇ with triethylaluminium taken in the mole ratio

: AlEt₃ = 10 : (10-14), respectively, in the presence of zirconacene dichloride Cp₂ZrCl₂ as catalyst taken in the amount 2-6 mole% with respect to 1-substituted allene. Reaction is carried out in argon atmosphere, at the room temperature under atmosphere pressure in methylene chloride as a solvent for 5 h followed by addition at temperature -5 C monochloride of copper taken in the amount 2-6 mole% to the parent allene and aldehyde RCHO where R means CH₃, n-C₃H₇ taken in an equimole amount with respect to AlEt₃. Then reaction mass is stirred for 6-8 h at the room temperature. Method ensures to synthesize 1,3-dialkyl-2-(n-propyl)-prop-2Z- 1-ols with high regio- and seteroselectivity that can be used in fine organic synthesis, production of paint and varnish materials, perfume substances, insect pheromones and biologically active substances. EFFECT: improved method of synthesis. 1 tbl, 1 ex

Description

,
где R - CH₃, н-C₃H₇;
R¹ - н-C₆H₁₃, н-C₈H₁₇
Спирты с Z-тризамещенной двойной связью и их производные могут найти применение в тонком органическом синтезе, а также в производстве лакокрасочных материалов, душистых веществ, феромонов насекомых, биологически активных веществ.The invention relates to the field of organic chemistry, in particular, to a method for producing 1,3-dialkyl-2- (n-propyl) -prop-2Z-en-1-tins of the general formula (1):

,
where R is CH ₃ , n-C ₃ H ₇ ;
R ¹ - n-C ₆ H ₁₃ , n-C ₈ H ₁₇
Alcohols with a Z-trisubstituted double bond and their derivatives can be used in fine organic synthesis, as well as in the manufacture of paints and varnishes, aromatic substances, insect pheromones, biologically active substances.

где n=8, 10; R - C₄H₉
Известным способом не могут быть получены вторичные спирты (1), содержащие Z-тризамещенную двойную связь.The known method ([1], Fyles TM, Lernoff CC, Weatherston J. The use of polymer supports in organic synthesis. XII. The total stereoselective synthesis of cis insect sex attractants on solid phase. Can. J. Chem., 1977, v . 55, 23, pp. 4135-4143) for the preparation of alcohols with a Z-disubstituted double bond by hydroboration of alkin-1-lov with 9-borabicyclo [3.3.1] nonane (9-BBN) followed by hydrolysis of the reaction mixture with acetic acid according to the scheme :

where n = 8, 10; R - C ₄ H ₉
In a known manner, secondary alcohols (1) containing a Z-trisubstituted double bond cannot be obtained.

где n=5, 7, 9; R - C₂H₅, н-C₄H₉, н-С₆Н₁₃
Известный способ не позволяет получать вторичные спирты (1), содержащие Z-тризамещенную двойную связь.The known method ([2], Ishmuratov G.Yu., Belezina G.G., Odinokov V.N., Zelenova L.M., Tolstikov G.A. New one-step way of stereospecific synthesis of (Z) -alken-1-ol from acetylene aldehydes. Izv. AN SSSR, Ser. Khim., 1983, 3, 671-672) for the preparation of primary alcohols with a Z-disubstituted double bond by hydroboration of acetylene aldehydes with 9-borabicyclo [3.3.1] nonane followed by hydrolysis of the reaction mixtures of acetic acid according to the scheme:

where n = 5, 7, 9; R - C ₂ H ₅ , n-C ₄ H ₉ , n-C ₆ H ₁₃
The known method does not allow to obtain secondary alcohols (1) containing a Z-trisubstituted double bond.

 An improved method for producing 1,3-dialkyl-2- (n-propyl) -prop-2Z-en-1-tins is proposed.

где R¹ - н-С₆Н₁₃, н-C₈H₁₇, с триэтилалюминием (АlЕt₃), взятыми в мольном соотношении

10:(10-14), предпочтительно 10:12, в присутствии катализатора цирконацендихлорида (Cp₂ZrCl₂) в количестве 2-6 мол.% по отношению к 1-замещенному аллену, предпочтительно 4 мол.%, в атмосфере аргона при комнатной температуре (~20^oС) и атмосферном давлении в хлористом метилене (СН₂Сl₂) в качестве растворителя в течение 5 ч с последующим добавлением при -5^oС катализатора однохлористой меди (CuCl) в количестве 2-6 мол.% по отношению к исходному аллену, предпочтительно 4 мол. %, и альдегида общей формулы RCHO, где R - СН₃, н-С₃Н₇, в эквимольном по отношению к АlЕt₃ количестве с перемешиванием реакционной массы 6-8 ч, предпочтительно 7 ч, при комнатной температуре (~20^oС). Кислотный гидролиз реакционной смеси приводит к 1,3-диалкил-2-(н-пропил)-проп-2Z-ен-1-олам (1) с выходом 66-84%. Реакция протекает по схеме:

где R - СН₃, н-С₃H₇; R¹ - н-C₆H₁₃, н-C₈H₁₇
Вторичные спирты (1) с Z-тризамещенной двойной связью образуются только лишь с участием АlЕt₃, терминальных алленов, альдегидов и циркониевого катализатора Cp₂ZrCl₂ с последующим окислением реакционной массы и кислотным гидролизом. В присутствии других соединений алюминия (например, Bu₂ ⁱAlCl, Bu₃ ⁱАl, Bu₂ ⁱAlH, EtAlCl₂, Et₂AlCl), других алленов (например, интернальных), других карбонильных соединений (например, кетонов) или другого катализатора (например, Zr(acac)₄, ZrCl₄, Cp₂TiCl₂, Pd(acac)₂, Ni(acac)₂, NiCl₂, Fe(acac)₂) целевые продукты (1) не образуются.The essence of the method consists in the interaction of terminal allens of the General formula

where R ¹ - n-C ₆ H ₁₃ , n-C ₈ H ₁₇ , with triethylaluminum (AlEt ₃ ), taken in a molar ratio

10: (10-14), preferably 10:12, in the presence of a catalyst of zirconacene dichloride (Cp ₂ ZrCl ₂ ) in an amount of 2-6 mol.% In relation to the 1-substituted allene, preferably 4 mol.%, In an argon atmosphere at room temperature (~ 20 ^o C) and atmospheric pressure in methylene chloride (CH ₂ Cl ₂ ) as a solvent for 5 hours, followed by the addition of a catalyst of monochloride copper (CuCl) in an amount of 2-6 mol.% at -5 ^o C to the starting allen, preferably 4 mol. %, and the aldehyde of the general formula RCHO, where R is CH ₃ , n-C ₃ H ₇ , in an amount equimolar to АlЕt _3, with stirring of the reaction mixture for 6-8 hours, preferably 7 hours, at room temperature (~ 20 ^o С ) Acid hydrolysis of the reaction mixture leads to 1,3-dialkyl-2- (n-propyl) -prop-2Z-en-1-olam (1) with a yield of 66-84%. The reaction proceeds according to the scheme:

where R is CH ₃ , nC ₃ H ₇ ; R ¹ - n-C ₆ H ₁₃ , n-C ₈ H ₁₇
Secondary alcohols (1) with a Z-trisubstituted double bond are formed only with the participation of AlEt ₃ , terminal allens, aldehydes and a zirconium catalyst Cp ₂ ZrCl ₂ , followed by oxidation of the reaction mass and acid hydrolysis. In the presence of other aluminum compounds (e.g., Bu ₂ ⁱ AlCl, Bu ₃ ⁱ Al, Bu ₂ ⁱ AlH, EtAlCl ₂ , Et ₂ AlCl), other allens (e.g. internal), other carbonyl compounds (e.g. ketones), or another catalyst (for example, Zr (acac) ₄ , ZrCl ₄ , Cp ₂ TiCl ₂ , Pd (acac) ₂ , Ni (acac) ₂ , NiCl ₂ , Fe (acac) ₂ ) the target products (1) are not formed.

The reaction in the presence of catalysts Cp ₂ ZrCl ₂ and CuCl more than 6 mol. % does not lead to a significant increase in the yield of target products (1). The use of catalysts Cp ₂ ZrCl ₂ or CuCl less than 2 mol.% Reduces the yield of 1,3-dialkyl-2- (n-propyl) -prop-2Z-en-1-tins (1), which is possibly associated with a decrease catalytically active centers in the reaction mass. The reaction was carried out at room temperature (~ 20 ^o C). At a higher temperature (for example, 40 ^o C) there is no significant increase in the yield of the target products, and at a lower temperature (for example, 0 ^o C) the reaction rate decreases.

A change in the ratio of the starting reagents in the direction of increasing the content of AlEt ₃ relative to the starting 1-substituted allene does not lead to a significant increase in the yield of the target products (1).

 Reactions were carried out using methylene chloride as a solvent. In other solvents (for example, aliphatic or aromatic), the regioselectivity of the reaction decreases.

триэтилалюминий (AlEt₃), альдегиды (RCHO), реакция протекает в присутствии катализатора (Cp₂ZrCl₂) и CuCl.Significant differences of the proposed method:
1. In the proposed method, terminal allens are used as starting compounds

triethylaluminum (AlEt ₃ ), aldehydes (RCHO), the reaction proceeds in the presence of a catalyst (Cp ₂ ZrCl ₂ ) and CuCl.

 In the known method, acetylene aldehydes and 9-borabicyclo [3.3.1] nonane are used as starting reagents, which restores the disubstituted triple bond.

 The proposed method has the following advantages.

 The method allows to obtain with high regio- and stereoselectivity 1,3-dialkyl-2- (n-propyl) -prop-2Z-en-1-oly (1), the synthesis of which is not described in the literature.

 The method is illustrated by the following examples.

Example. In a 50 ml glass reactor mounted on a magnetic stirrer, 10 ml of methylene chloride (CH ₂ Cl ₂ ), 10 mmol of 1,2-nonadiene, 0.4 mmol of catalyst Cp ₂ ZrCl ₂ , at ~ 0 ^o С are placed in an argon atmosphere 12 mmol Et ₃ Al, stirred for 5 hours at room temperature (~ 20 ^° C), 0.4 mmol of CuCl catalyst and 12 mmol of oil aldehyde (nC ₃ H ₇ CHO) were added at -5 ^° C, stirred for 7 hours ( ~ 20 ^o C), hydrolyze ~ 10% Hcl. 5-propyldodec-5Z-en-4-ol is isolated from the organic layer in 76% yield.

ИК-спектр (ν, см^-1): 2950, 2930, 2860, 1450, 1380, 960, 720.Spectral characteristics of 5-propyldodec-5Z-en-4-ol (1):

IR spectrum (ν, cm ^-1 ): 2950, 2930, 2860, 1450, 1380, 960, 720.

¹ H NMR Spectrum (δ, ppm): 0.77-0.98 (m, 9H, CH ₃ ); 1.04-1.38 (m, 10H, CH ₂ ); 1.48-1.78 (m, 4H, CH ₂ ); 1.90-2.33 (m, 4H, CH ₂ C = C); 3.34-3.55 (m, 1H, OH); 4.05-4.31 (m, 2H, CH ₂ O); 5.04-5.91 (m, 1H, CH = C). ¹³ C NMR spectrum (δ, ppm): 13.76 q (C ¹ ), 18.57 t (C ² ), 37.04 t (C ³ ), 71.72 d (C ⁴ ), 138 10 s (C ⁵ ), 127.37 d (C ⁶ ), 29.50 t (C ⁷ ), 29.11 t (C ⁸ ), 29.95 t (C ⁹ ), 31.90 t (C ¹⁰ ), 22.74 t (C ¹¹ ), 14.04 k (C ¹² ), 36.39 t (C ¹³ ), 22.34 t (C ¹⁴ ), 14.15 k (C ¹⁵ ).

 Other examples confirming the method are given in the table.

Claims (1)

The method of obtaining 1,3-dialkyl-2- (n-propyl) -prop-2Z-en-1-ol of the General formula

where R is CH ₃ , n-C ₃ H ₇ ;
R ^' is n-C ₆ H ₁₃ , n-C ₈ H ₁₇ ,
characterized in that the terminal allens of the general formula

wherein R ^'-n-C ₆ H _13, n-C ₈ H _17,
interact with triethylaluminum in a molar ratio

in the presence of a catalyst of zirconacene dichloride Cp ₂ ZrCl ₂ taken in an amount of 2-6 mol. % relative to the 1-substituted allene, in an argon atmosphere at room temperature and atmospheric pressure in methylene chloride as a solvent for 5 hours, followed by the addition of copper monochloride catalyst at -5 ^° C in an amount of 2-6 mol. % to the starting allene and aldehyde of the formula
RCHO,
where R is CH ₃ , nC ₃ H ₇ ,
in an equimolar amount with respect to AlEt ₃ , after which the reaction mass is stirred for 6-8 hours at room temperature.

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