SU771090A1 - Method of preparing tertiary alkylthienine alcohols - Google Patents

Description

one

This invention relates to an improved process for the preparation of tertiary alkylthioenin alcohols of general formula 1.

L1

(J (iai (i (,

/ Rt

HE

- lower alkyl,

R rj

Where

independently of each other - lower alkyl or cycloalkyl,

which are used as intermediates in organic synthesis.

There is one known method for the preparation of tertiary alkylthioinic alcohols of general formula I, which consists in the fact that diacetylene alcohol of general formula

RI

(i (,

where R and RJ have the indicated values, they are reacted with alkyl mercaptan in methanol in the presence of alkali at 02-C. The yield of the target product is 72% fl. The disadvantages of this method are the relatively low yield of the target product and the need for preliminary preparation of explosive diacetylenic alcohols.

The purpose of the invention is to increase the target product and simplify the process, eliminating the use of explosive source compounds.

The aim is achieved by the use of the Elm method for the preparation of tertiary alkylthioinic alcohols of general formula I, in that diacetylene is reacted with a ketone of general formula E

RI.

(i o

/

Vg

where R and K-g have the indicated meanings,

followed by treatment with alkyl mercaptane 25 tane in liquid ammonia in the presence of

alkalis at temperature, (-30) - (- 45fc.

The yield of the target product 82-95%. The hallmark of the method

is carrying out the process by way of 30 reacting diacetylene with a ketone of the general formula, followed by treatment with alkyl mercaptan in liquid ammonia at a temperature of (-30) - (- 45) C. The process proceeds according to the following scheme H (ls ((jH + EjBz "io 2S.Fi ( idse (J-na (iririH a / OH) The reaction is carried out in the presence of 0.05-0.08 moles of alkali metal hydroxide (calculated as diacetylene) with a 6-10% solution of diacetylene in liquid ammonia for 4- 8 h with a molar ratio of diacetylene ketone and thiol equal to 1: (0.5-1) g (1-1 An excess of diacetylene relative to ketone is necessary in order to direct the reaction towards the formation of diacetylene alcohol and exclude the possibility of obtaining diacetylene glycols. An alkali metal hydroxide catalyzes the condensation of diacetylene with ketone and accelerates the reaction of diacetylene alcohol with thiol, which is taken in a small excess, the method used to isolate the tertiary alkylthylenomers. 82-95%. As a by-product of the preparation of 1-alkylthio-1-butene-3-yns (11a-11d1, the yield of which is 20-30% based on taken diacetylene. Example 1..2-Methyl-b-ethylthio-5-hexene-3-yn-2-ol (1a). a) To a solution of 7.4 g (0.148 mol) of diacetylene in 100 ml of liquid ammonia, 0.49 g (0.012 mol) of powdered caustic soda and 5.72 (0.098 mol) of acetone are added. The mixture was stirred at (-3Q) (-32) ° C for 4 hours, 12.82 g (o, 207 mol) ethanethiol (diacetylene-acetone-thiol ratio 1: 0.67: 1.4) and stir 4 more. Ammonia and diacetylene evaporating during the reaction are collected in a cooled trap and returned to the reactor. At the end of the experiment, ammonia is evaporated and collected in a trap. To remove the catalyst, the residue is diluted with ether and passed through a bed (1.52 cm) of AEjO. After the ether has been removed by distillation, 4.74 g (28.6% of B is calculated per taken diacetylene) and gH a thio esters, b.p. 35-38 s / 1.5 mmHg Pg5 ° 1.5421, and 13.84 g (82.6% per acetone) of alcohol 1a bp. 125-128C / 1.5 mmHg , p 1,5385. b) To a solution of 4.2 g (0.084 mol) of diacetylene in 60 ml of liquid ammonia 0.28 g (0.007 mol) of powdered caustic soda, 4.87 g (0.084 mol) of acetone are added, stirred for 3 hours at (-30)), 6.24 g (0.1 mol) of ethanethiol (diacetylene-acetone-thiol ratio 1: 1: 1.2) is added and stirred for another 3 hours. After the completion of the reaction, ammonia is evaporated, the residue is dissolved in ether, passed through a layer (1.5-2 cm), distillation isolated 0.83 g (8.8% based on the diacetylene taken) of the thioether aa, t. Bale. 3638/1, 5 mmHg, p 1.5418, and 11.69 g (81.9% based on the taken diacetylene) alcohol 1 a, b.p. 99-102 C / 1 mmHg, p 1.5371. Example 2. Z-Methyl-7-ethylthio-b-hepten-4-in-3 ol (I b-). A solution of 5.15 g (0.103 mol) of diacetylene in 68 ml of liquid ammonia, 0.36 g (0.009 mol) of powdered caustic soda and 4.95 g (0.068 mol) of methyl ethyl ketone are stirred for 3 hours at (-30) - (- 32) c, 7.67 g (0.124 mol) of ethanethiol (diacetylene-ketone-thiol ratio 1: 0.67: 1.2) are added and stirred for another 3 hours. After evaporation of the ammonia, the residue is diluted with ether, passed through a layer (1, 52 cm), distillation isolated 2.94 g (25.9% based on the taken diacetylene) of the thioether jj a, b.p. 3538 ° C / 1, 5 mmHg, 1.5424, and 12.11 g (95.7% based on the total ketone) of alcohol 16, bp. 110ISS / mmHg, p 1.5378. Example 3. Synthesis of 4- (1-hydroxycyclopentyl-1-ethylthio-1-butene-3-yna (1c). A solution of 5.19 g (0.104 mol). Diacetylene in 70 ml of liquid ammonia, 0.36 g (0.009 mol a) powdered sodium hydroxide and 5.81 g (0.069 mol) of cyclopentanone are stirred for 3 hours at (-30) - (- 32) ° C, then 7.78 g (0.0124 mol) of ethanethiol (ratio of diacetylene ketone-thiol 1: 0.66: 1.2) and stirred for another 3 hours. After evaporation of the ammonia, the residue was diluted with ether, passed through a 5 if 2-2 cm layer and 3.48 g (30% based on taken diacetylene) was isolated by distillation. thioether | a, t, kip. 31-33s / 1 mmHg, p 1.5429, and 11.37 g (83.9% based on the cyclopentanone used) alcohol I, b.p. 130-133s / 1 mm- Hg, p 1.5625. Example 4. 4- (l-Oxycyclohexyl) -l-ethylthio-l-buten-3-yne (1 g). 0.32 g (0.008 mol) of powdered sodium hydroxide, 6.58 g (0.067 mol) of cyclohexanone are added to a solution of 5 g (0.1 mol) of diacetylene in 67 ml of liquid ammonia, stirred for 3 hours at (-30) - ( -32) C, add 7.44 g (0.12 mol) of ethanethiol (diacetylene-ketone thiol ratio 1: 0.67: 1.2) and stir for another 3 hours. After the completion of the reaction, ammonia is evaporated, the residue is dissolved in ether, passed through a layer (1.52 cm), and distilled by distillation

3.07 g (27.4% calculated on the taken diacetylene) thioether Ia, b.p. ZO-ZZ S / mmHg, p 1.5420, and 12.32 g (88% based on the cyclohexanone taken) alcohol 1 g, b.p. 131-134 ° C / 1 mm Hg ., p 1,5629.

Example 5. 2-Methyl-b-propylthio-5-hexene-3-yn-2-ol (1d).

a) A solution of 5.92 .g (0.118 mol) of diacetylene in 80 ml of liquid ammonia 0.56 g (0.01 mol) of powdered caustic soda and 4.57 g (0.079 mol) of acetone is stirred for 3 hours at (-30) ( -32) ° C, then 10.8 g are added

(0,142 mol) of propanethiol (the ratio of diacetylene-ketone-thiol 1: 0,67:: 1,2) and stirred for another

3h After evaporation of the ammonia, the residue was diluted with ether, passed through a bed (1.5-2 cm) of AEgO-i and 3 g (20% calculated as diacetylene) of 1-propylthio-1-butene-3-yna ( PB) so kip. 56-59 ° C / 2 mmHP. P 1.5315, and 13.12 g (90.5 g per acetone) alcohol 1 bp, 100-103 ° C / 1 mm Hg. P

 1.5320.

b) To a solution of 6.5 g (0.13 mol) of dialen of lene in 90 ml of liquid ammonia, 0.43 g (0.011 mol) of powdered caustic soda, 5.08 g (0.087 mol) of acetone are added, stirred for 2 hours at ( -30) - (- 32), add

1-3.7 g (0.18 mol) of propanthiol (diacetylene-acetone-thiol ratio 1: 0.67: 1.4) and stirred for another 2. After evaporation of the ammonia, the residue is dissolved in ether, the layer (1.5 -2 cm) APa. O-distillation was used to extract 2.; 91 g (17.8% calculated on taken diacetylene) of thiospir S b, bp. 62-65 C / 3 mmHg, p

 1.5330, and 11.84 g (74.2% based on the taken diacetylene) alcohol I d k.p. 120-123C / 3 mmHg, p 1.5316.

c) A solution of 4 g (0.08 mol) of diacetylene in 60 ml of liquid ammonia,

0.16 g (0.004 mol) of a pore of Icoobrazny NaOH and 3.09 g (0.053 mol) of acetone are stirred for 3 hours at (-30) - (- 32) C, then 7.3 g (0.096 mol) of propanethiol (ratio diacetal-ketone-thiol 1: 0.66: 1.2) and stirred for another 3 hours. Ammonia is evaporated, the residue is diluted with ether, passed through a layer (1.5-2 cm), and 3.96 g are separated by distillation. (39.3% in planting diacetylene taken up) thioether f b, b.p. 55-57.5C / 2 mmHg, p 1.5338, and 5.81 g (59.3% per calculated acetone) alcohol 1 d,

bp 114-117s / 2 mm Hg.

,20

 1.5315.

Example 6. 2-Methyl-6-isopropylthio-5-hexene-3-yn-2-ol (1e).

a) To a solution of 5 g (0.1 mol) of diacetylene in 70 ml of liquid ammonia was added 0.32 g (0.008 mol) of powdered NaOH, 3.87 g (0.067 mol of acetone, stirred for 3 hours at (-30) (- 32) C, add 9.12 g, (0.12 mol) of isopropanethiol (diacetylene-acetone-thiol ratio 1: 0.67: 1.2) and stir for another 3 hours (ammonia and diacetylene condensed in the trap are returned to the reaction ) After evaporation of the ammonia, the residue was diluted with ether, passed through a layer (1.5-2 cm) and 3.44 g (27.3% based on taken diacetylene) 1-isopropylthio-1-butene-3 was distilled. -ain (HB), BP. 53-5bs / 1 mm Hg, g 1,5292, and 10.91 g (88.8% (based on acetone taken)) alcohol I e, bp 113-115 0/1 mm Hg,% "1.5291.

b) A solution of 5.7 g (0.114 mol) of diacetylene in 70 ml of liquid ammonia, 0.32 g (0.008 mol) of powdered caustic soda and 3.72 g (0.064 mol) of acetone is stirred for 3 hours at (-40) (-45 ) C, 9 g (0.118 mol) of isopropanethiol (diacetylene-ketone-thiol ratio 1: 0.56: 1) are added and stirred for an additional 3 hours at the same temperature. After completion of the reaction, ammonia was evaporated, the residue was diluted with ether, passed through a layer (1.52 cm) and 6.73 g (46.8% calculated on the taken diacetylene) of thioether f in, i.e. boiled out. 39-42 ° C / 0.5 mm Hg, p 1.5288, and 9.65 g (81.6% based on the taken ketone) of alcohol 1e, bp. 97100C / 0, 5 mm Hg, p 1.5288.

Example 7. 2-M $ tyl-6-butyl-5-hexene-3-yn-2-ol (1g).

a) To a solution of 4.3 g (0.086 mol) of diacetylene in 57 ml of liquid ammonia, 0.28 g (0.007 mol) of powdered sodium hydroxide, 3.32 g (0.057 mol) of acetone are added, and the mixture is stirred

3h at (-30) - (- 32) C, 9.28 g (0.103 mol) of butanethiol are added (the ratio of diacetylene to ketone-thiol

 1: 0,66: 1,2) and mix another 3h. Then, ammonia is evaporated, the residue is dissolved in ether, passed through a layer (1.5-2 cm) A, aO, and 3.44 g (28.5% based on zaato diacetylene) 1-butylthio- 1-buten-3-yna (f g), b.p. 6165s / 1 mmHg, pp 1.5250, and 9.8 g (86.4% in terms of kegon taken) of alcohol I, b.p. 116- ° 119s / 1 mm ipT.cT., 11 1.5252.

Claims (1)

b) A solution of 4.5 g (0.09 mol) of diacetylene in 60 ml of liquid ammonia, 0.4 g (0.007 mol) of powdered caustic potash, 3.49 g (0.06 mol) of the acetone is stirred for 3 hours at (- 30) - (-32) With the addition of 1 from 9.76 rt (0.108 mol) of butantiodt (diacetylene-ketone-thiol ratio 1: 0.66: 1.2) and stirring for another 3 hours. After evaporation of the ammonia, the residue is diluted with eff. , AtiO-i is passed through a layer (1.52 cm), 2.78 g (22% calculated on the taken diacetylene) of the thioether E g, b.p. 6164 C / 2 mmHg, p 1.5257, and 10.07 g (84.5% based on the taken ketone) of alcohol I; t, kip. 116119 ° С / 1 mmHg. 1,5252. Example 8. 2-Methyl-6-isobutylthio-5-hexene-3-in-2-ol (1h). A solution of 5 g (0.1 mol) of diacetyl in 67 ml of liquid ammonia, 0.32 g (0.008 mol) of powdered sodium hydroxide and 2.9 g (0.05 mol) of acetone are stirred for 3 hours at (-30) - ( -32) ° C. 12.6 g (0.14 mol) of isobutanethiol (a ratio of acetylene-ketone-thiol-1: 0.5: 1.4) are added and stirred for another 3.5 hours. After evaporation of the ammonia, the residue is diluted 4.77 g (34.1% based on diacetyl thioether, d.p. 56-59 C72 mm Hg 1.5230, are separated by ether through a layer (1.5-2 cm) of AljtOiH by distillation. and 8.17 g (82.5% based on a-calculated ketone) of alcohol I h, bp 114-117 ° C / 2 mm Hg, p 1.5233. Formula of the invention Production method and tertiary alkylienoic alcohols of the general formula Yes, for R where is lower alkyl, R and R are independently of each other lower alkyl or cycloalkyl using alkyl mercaptan and alkali, characterized in that, in order to increase the yield of the target product and simplify the process, diacetylene is reacted with a ketone of the general formula where R and Rj have the indicated meanings, followed by treatment of the obtained product with alkyl mercaptan in liquid ammonia at a temperature of (-30) - (- 45) C, Sources of information taken into account during the examination 1. Nick AN lska et al. Synthesis of tertiary 1-alkylthio-1-ene-3-in alcohols. IAN, a series of chem. 1977, 1403 (prototype).