Process for preparing an acetal from an olefin using an iodine-alkyl compound

Abstract

A method for producing acetal from olefin using an iodine-alkyl compound.

Description

Technology Field

[0001] The present invention relates to a method for producing acetal from olefin using an iodine-alkyl compound. Background Technology

[0002] The objective of the present invention was to provide a method for producing acetal from olefins. The problem to be solved

[0003] We aim to achieve a good yield here. means of solving the problem

[0004] The above objective is achieved by the method according to claim 1.

[0005] Method including the following steps:

[0006] a) A step of initially charging olefins;

[0007] b) Step of adding a compound of the following chemical formula (I):

[0008]

[0009] Here, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 -H, -(C1-C 12 )-alkyl, -(C6-C 20 )-Selected from Aryl;

[0010] R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 This -(C6-C 20 In the case of )-aryls, the aryl ring is -(C1-C 12 )-alkyl, -O-(C1-C 12 May have a substituent selected from )-alkyl;

[0011] c) a step of adding a Pt compound selected from Pt(II)(COD)Me2, diphenyl(1,5-COD)Pt(II), Pt(II)(acac)2, Pt(O)(PPh3)4, Pt(O)(DVTS) solution (CAS: 68478-92-2), Pt(O)(ethylene)(PPh3)2, tris(benzylideneacetone)Pt(O), Pt(II)(OAC)2 solution, Pt(O)(t-Bu)2, and Pt(II)(hexafluoroacetylacetonate)2;

[0012] d) a step of adding an iodine-alkyl compound;

[0013] e) a step of adding an alcohol selected from methanol, ethanol, 1-propanol, 1-butanol, 1-pentanol, 1-hexanol, 1-heptanol, 1-octanol, ethane-1,2-diol, propane-1,2-diol, propane-1,3-diol, and butane-1,4-diol;

[0014] f) a step of supplying CO and H2;

[0015] g) a step of heating the reaction mixture from steps a) to f) to convert the olefin into an acetal.

[0016] In this method, method steps a) through f) may be performed in any preferred order. However, typically, CO and H2 are added after the co-reactants are initially charged in steps a) through e). Specific details for implementing the invention

[0017] (C1-C 12 The expression )-alkyl encompasses straight-chain and branched alkyl groups having 1 to 12 carbon atoms. These are preferably (C1-C8)-alkyl groups, more preferably (C1-C6)-alkyl, and most preferably (C1-C4)-alkyl.

[0018] Suitable (C1-C 12)-alkyl groups are particularly methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, 2-pentyl, 2-methylbutyl, 3-methylbutyl, 1,2-dimethylpropyl, 1,1-dimethylpropyl, 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 2-hexyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 2,2-dimethylbutyl, 1,3-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethylbutyl, 1-ethyl-2-methylpropyl, n-heptyl, 2-heptyl, 3-heptyl, 2-ethylpentyl, 1-propylbutyl, n-octyl, 2-ethylhexyl, 2-propylheptyl, nonyl, and decyl.

[0019] (C6-C 20 The expression )-aryl encompasses mono- or polycyclic aromatic hydrocarbyl radicals having 6 to 20 carbon atoms. These are preferably (C6-C 14 )-aryl, more preferably (C6-C 10 )-It is Aril.

[0020] Suitable (C6-C 20 The )-aryl group is particularly phenyl, naphthyl, indenyl, fluorenyl, anthracenyl, phenanthrenyl, naphthacenyl, crisenyl, pyrenyl, and coronenyl. Preferred (C6-C 20 The )-aryl groups are phenyl, naphthyl, and anthracenyl.

[0021] In one variation of the method, R 2 , R 3 , R 5 , R 6 , R 7 , R 8 -(C1-C 12 )-alkyl, -(C6-C 20 )-Selected from Aril.

[0022] In one variation of the method, R 5 , R 6 , R 7 , R 8-(C6-C 20 )-It is Aril.

[0023] In one variation of the method, R 5 , R 6 , R 7 , R 8 is -Ph.

[0024] In one variation of the method, R 2 and R 3 -(C1-C 12 )-alkyl.

[0025] In one variation of the method, R 2 and R 3 It is -CH3.

[0026] In one variation of the method, R 1 and R 4 is -H.

[0027] In one variation of the method, compound (I) has structural formula (1):

[0028] .

[0029] In one variation of the method, the Pt compound is Pt(II)(COD)Me2.

[0030] In one variation of the method, the iodine-alkyl compound is selected from ICH2CH2I, CH3I, CH2I2, CHI3, CI4, I2CHCHI2, I3CCI3, ICH2CH2CH2I, ICH2CH2CH2CH2I, and ICH2CH2CH2CH2CH2I.

[0031] In one variation of the method, the iodine-alkyl compound is selected from ICH2CH2I and CH3I.

[0032] In one variation of the method, the iodine-alkyl compound is ICH2CH2I.

[0033] In one variation of the method, the iodine-alkyl compound is CH3I.

[0034] In one variation of the method, the alcohol in step e) of the method is selected from methanol, ethanol, 1-propanol, 1-butanol, ethane-1,2-diol, and propane-1,2-diol.

[0035] In one variation of the method, the alcohol in step e) of the method is MeOH.

[0036] In one variation of the method, CO and H2 are supplied at a pressure ranging from 1 MPa (10 bar) to 6 MPa (60 bar).

[0037] In one variation of the method, CO and H2 are supplied at a pressure ranging from 3 MPa (30 bar) to 5 MPa (50 bar).

[0038] In one variation of the method, the reaction mixture is heated to a temperature in the range of 50°C to 150°C.

[0039] In one variation of the method, the reaction mixture is heated to a temperature in the range of 70°C to 130°C.

[0040] In one variation of the method, the olefin is selected from ethene, propene, 1-butene, cis- and / or trans-2-butene, isobutene, 1,3-butadiene, 1,2-butadiene, 1-pentene, cis- and / or trans-2-pentene, 2-methyl-1-butene, 3-methyl-1-butene, 2-methyl-2-butene, hexene, tetramethylethylene, heptene, 1-octene, 2-octene, di-n-butene, tri-n-butene, 1,7-octadiene, 1,9-decadien, methyl 9-decenoate (9-Dame) or a mixture thereof.

[0041] In one variation of the method, the olefin has two double bonds.

[0042] In one variation of the method, the olefin has two terminal double bonds.

[0043] In one variation of the method, this method is an additional method step f')

[0044] f') Step of adding a non-alcohol solvent

[0045] Includes

[0046] In one variation of the method, the solvent is selected from THF, MTBE, DCM, ACN, heptane, DMF, toluene, xylene, mesitylene, and dibenzyltoluene.

[0047] The present invention will be described in detail below with reference to working embodiments.

[0048] General experimental description

[0049] Olefins, inert solvents, alcohols, Pt compounds, ligands, and halogen compounds are placed in a stainless steel autoclave from Parr Instruments under argon. Synthesis gas CO / H2 (1:1) is injected, and the reaction is carried out at a selected reaction temperature while stirring. After the reaction time is finished, the autoclave is cooled to room temperature, the residual pressure is released, and a GC sample is taken and analyzed to determine the yield of the target product.

[0050]

[0051] 4.1 mmol of butadiene (3.2 ml of 8.3% stock solution in toluene), 80 mmol of MeOH (3.2 ml), 7 ml of toluene, 1.2 mol% of Pt(II)(COD)Me2 (16.7 mg), 1.2 mol% of Xantphos (1) (29 mg), and 1.2 mol% of XCH2CH2X or 2.4 mol% of CH3X are introduced into a 25 ml autoclave from Parr under argon. Synthesis gas CO:H2 = 1:1 is injected at 40 bar, and the mixture is heated. The reaction is carried out while stirring. After the reaction is finished, the autoclave is cooled, the pressure is released, and the reaction solution is transferred to a Schlenk vessel. 10 ml of CH2Cl2 (0.6 ml) is added, and 1 H NMR analysis and GC analysis were performed.

[0052] Reaction conditions:

[0053] 4.1 mmol butadiene, 1.2 mol% Pt(II)(COD)Me2, 1.2 mol% xanthophos (1), solvent: toluene, alcohol: MeOH, p(CO / H2): 40 bar (4 MPa).

[0054] The results of these experiments are listed in the table below.

[0055] Halogen variation

[0056]

[0057] Modification of iodine-alkyl compounds

[0058]

[0059] As indicated by the experimental results, the above objective is achieved by the method according to the present invention.

Claims

Claim 1 A method comprising the following steps: a) a step of initially charging an olefin; b) a step of adding a compound of the following formula (I): Here, R 1 , R 2 , R 3 , R 4 is -H, -(C1-C 12 )-alkyl, -(C6-C 20 )-Selected from aryl;R 5 , R 6 , R 7 , R 8 -(C6-C 20 )-Ariligo;R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 This -(C6-C 20 In the case of )-aryls, the aryl ring is -(C1-C 12 )-alkyl, -O-(C1-C 12 c) may have a substituent selected from )-alkyl; d) a step of adding a Pt compound selected from Pt(II)(COD)Me2, diphenyl(1,5-COD)Pt(II), Pt(II)(acac)2, Pt(O)(PPh3)4, Pt(O)(DVTS) solution (CAS: 68478-92-2), Pt(O)(ethylene)(PPh3)2, tris(benzylideneacetone)Pt(O), Pt(II)(OAC)2 solution, Pt(O)(t-Bu)2, Pt(II)(hexafluoroacetylacetonate)2; e) a step of adding an iodine-alkyl compound; e) methanol, ethanol, 1-propanol, 1-butanol, 1-pentanol, 1-hexanol, 1-heptanol, 1-octanol, A step of adding an alcohol selected from ethane-1,2-diol, propane-1,2-diol, propane-1,3-diol, and butane-1,4-diol; f) a step of supplying CO and H2; g) a step of heating the reaction mixture from steps a) to f) to convert the olefin into an acetal. Claim 2 In paragraph 1, R 2 and R 3 This -(C1-C 12 )-alkyl, -(C6-C 20 )-A method selected from Aryl. Claim 3 In paragraph 1 or 2, R 2 and R 3 This -(C1-C 12 )-alkyl method. Claim 4 In paragraph 1 or 2, R 1 and R 4 A method where -H. Claim 5 A method according to claim 1 or 2 in which the compound (I) has the following structural formula (1): . Claim 6 A method according to claim 1 or 2, wherein the Pt compound is Pt(II)(COD)Me2. Claim 7 A method according to claim 1 or 2, wherein the iodine-alkyl compound is selected from ICH2CH2I, CH3I, CH2I2, CHI3, CI4, I2CHCHI2, I3CCI3, ICH2CH2CH2I, ICH2CH2CH2CH2I, ICH2CH2CH2CH2CH2I. Claim 8 A method according to claim 1 or 2, wherein the iodine-alkyl compound is selected from ICH2CH2I, CH3I. Claim 9 A method according to claim 1 or 2, wherein the iodine-alkyl compound is ICH2CH2I. Claim 10 A method according to claim 1 or 2, wherein the iodine-alkyl compound is CH3I. Claim 11 A method according to claim 1 or 2, wherein the alcohol in step e) of the method is selected from methanol, ethanol, 1-propanol, 1-butanol, ethane-1,2-diol, and propane-1,2-diol. Claim 12 A method according to claim 1 or 2, wherein the alcohol in step e) of the method is MeOH. Claim 13 The method of claim 1 or 2, wherein the olefin is selected from ethene, propene, 1-butene, cis- and / or trans-2-butene, isobutene, 1,3-butadiene, 1,2-butadiene, 1-pentene, cis- and / or trans-2-pentene, 2-methyl-1-butene, 3-methyl-1-butene, 2-methyl-2-butene, hexene, tetramethylethylene, heptene, 1-octene, 2-octene, di-n-butene, tri-n-butene, 1,7-octadiene, 1,9-decadien, methyl 9-decenoate (9-Dame), or a mixture thereof. Claim 14 delete

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