AU2018100826A4 - Organic synthesis intermediates 4-iodobenzaldehyde synthesis method - Google Patents

Organic synthesis intermediates 4-iodobenzaldehyde synthesis method Download PDF

Info

Publication number
AU2018100826A4
AU2018100826A4 AU2018100826A AU2018100826A AU2018100826A4 AU 2018100826 A4 AU2018100826 A4 AU 2018100826A4 AU 2018100826 A AU2018100826 A AU 2018100826A AU 2018100826 A AU2018100826 A AU 2018100826A AU 2018100826 A4 AU2018100826 A4 AU 2018100826A4
Authority
AU
Australia
Prior art keywords
solution
added
iodobenzaldehyde
controlled
temperature
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
AU2018100826A
Inventor
genan guan
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Chengdu Qianye Longhua Petroleum Engineering Technology Consulting Co Ltd
Original Assignee
Chengdu Qianye Longhua Petroleum Engineering Technology Consulting Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Chengdu Qianye Longhua Petroleum Engineering Technology Consulting Co Ltd filed Critical Chengdu Qianye Longhua Petroleum Engineering Technology Consulting Co Ltd
Application granted granted Critical
Publication of AU2018100826A4 publication Critical patent/AU2018100826A4/en
Ceased legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C07C45/29—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of hydroxy groups

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)

Abstract

Organic synthesis intermediates 4-iodobenzaldehyde synthesis method Abstract 5 The present invention discloses organic synthesis intermediates 4-iodobenzaldehyde synthesis method, comprises the following steps: 2-amino-4-iodine benzyl alcohol, sodium sulfate solution were added to the reaction vessel, controlled the temperature of the solution, controlled the stirring speed, reacted, added ethyl butyl ether solution, continued to react; added 1, 4-amyl lactone solution, 10 added palladium nitrate powder in batch, when finished raising the temperature of the solution, controlled the stirring speed, back-flow, reacted, reduced the temperature of the solution, added potassium nitrate solution, set aside, stratified solution, separated reservoir, washed with the sodium bromide solution, washed with the N-ethyl acetamide solution, re-crystallized in the 2-ethanolamine solution, dehydrated with 15 dehydration, got the finished product 4-effect of formaldehyde. Figure 1 0 35o 3000 2500 205 00 1000 500 Figure I

Description

The present invention discloses organic synthesis intermediates
4-iodobenzaldehyde synthesis method, comprises the following steps: 2-amino-4-iodine benzyl alcohol, sodium sulfate solution were added to the reaction vessel, controlled the temperature of the solution, controlled the stirring speed, reacted, added ethyl butyl ether solution, continued to react; added 1, 4-amyl lactone solution, added palladium nitrate powder in batch, when finished raising the temperature of the solution, controlled the stirring speed, back-flow, reacted, reduced the temperature of the solution, added potassium nitrate solution, set aside, stratified solution, separated reservoir, washed with the sodium bromide solution, washed with the N-ethyl acetamide solution, re-crystallized in the 2-ethanolamine solution, dehydrated with dehydration, got the finished product 4-effect of formaldehyde.
Figure 1
2018100826 19 Jun 2018
1/1
Figure AU2018100826A4_D0001
Figure 1
2018100826 19 Jun2018
Organic synthesis intermediates 4-iodobenzaldehyde synthesis method
FIELD OF THE INVENTION
The present invention relates to a method for preparing a pharmaceutical 5 intermediate which belongs to the field of organic synthesis, more particularly, relates to organic synthesis intermediates 4-iodobenzaldehyde synthesis method.
GENERAL BACKGROUND
4-iodobenzaldehyde is a kind of synthesis intermediates about organic synthesis, 10 most of the existing synthesis methods are using chromium chloride and carbon tetrachloride as reactants, but chromium chloride seriously polluted the environment, it has the higher processing cost of pollution in the process of reaction, carbon tetrachloride belongs to colorless toxic liquid, the synthetic solvents will increase the risk factor of the reaction process, it does not comply with the green chemistry and environmental protection request, and the synthesis method is complicated. Therefore, it is necessary to propose a new synthesis method.
SUMMARY
Based on the technical problems of the background technology, the purpose of 20 the present invention is to provide organic synthesis intermediates
4-iodobenzaldehyde synthesis method, comprises the following steps:
A: 2-amino-4-iodine benzyl alcohol, 1.8 L sodium sulfate solution were added to the reaction vessel, controlled the temperature of the solution to 20-26 °C, controlled the stirring speed at 210-240 rpm, reacted for 80-110min, added 700ml ethyl butyl ether solution, continued to react for l-2h;
B: added 1,4-amyl lactone solution, added palladium nitrate powder in batches, when finished raising the temperature of the solution to 30-35°C, controlled the stirring speed at 310-350rpm, back-flow, reacted for 90-110 min, reduced the temperature of the solution to 5-9°C,added 800ml potassium nitrate solution, set aside
2-3h, stratified solution, separated reservoir, washed with the sodium bromide
2018100826 19 Jun 2018 solution, washed with the N-ethyl acetamide solution, re-crystallized in the 2-ethanolamine solution, dehydrated with dehydration, got the finished product 4 - iodobenzal dehy de.
Preferably, the sodium sulfate solution has a mass fraction of 10-15%.
Preferably, the mass fraction of the ethyl butyl ether solution is 20-26%.
Preferably, the 1, 4-amyl lactone solution has a mass fraction of 40-45%. Preferably, the potassium nitrate solution has a mass fraction of 15-22%. Preferably, the mass fraction of sodium bromide solution is 10-16%.
Preferably, the N-ethyl acetamide solution has a mass fraction of40-47%.
Preferably, the mass fraction of 2-ethanolamine solution is 80-85%.
Throughout the reaction process can be the following reaction formula:
CHO ch2oh
Figure AU2018100826A4_D0002
Pb(NO3)3 + C5li3o2 -J
ΓΊ
I
Compared with the synthetic method disclosed in the background art, the invention provides organic synthesis intermediates 4-iodobenzaldehyde synthesis method, it is unnecessary to use chromium chloride and carbon tetrachloride as reactants, this method can avoid the environmental pollution of chromium chloride and decease tlie processing cost of pollution in the process of reaction, at the same time, avoid the risk of carbon tetrachloride as a toxic liquid to increase the risk coefficient of the reaction process so that it meets the requirements of green environmental protection, reduce intermediate links reaction, decrease the reaction time and improve the reaction yield, at the same time, tlie present invention provides a new synthetic route which has laid a good foundation for further enhancing the yield of the reaction.
2018100826 19 Jun 2018
DESCRIPTION OF THE DRAWINGS
Figure 1 is the infrared analysis spectrum of finished product 4- io dobenzaldehyde.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
The following examples with reference to specific embodiments of the present invention are further illustrated:
Embodiment 1
Organic synthesis intermediates 4-iodobenzaldehyde synthesis method, comprises the following steps:
A: 3mol 2-amino-4-iodine benzyl alcohol, 1.8L sodium sulfate solution with a mass fraction of 10% were added to the reaction vessel, controlled the temperature of the solution to 20°C, controlled the stirring speed at 210 rpm, reacted for 80min,added 700ml ethyl butyl ether solution with a mass fraction of 20%, continued to react for lh;
B: added 3mol 1,4-amyl lactone solution with a mass fraction of 40%, added 3mol palladium nitrate powder in three times, when finished raising the temperature of the solution to 30 °C, controlled the stirring speed at 310rpm, back-flow, reacted for 90min, reduced the temperature of the solution to 5 °C,added 800ml potassium nitrate solution with a mass fraction of 15%, set aside 2h, stratified solution, separated reservoir, washed with the sodium bromide solution with a mass fraction of 10%, washed with the N-ethyl acetamide solution with a mass fraction of 40%, re-crystallized in the 2-ethanolamine solution with a mass fraction of 80%, dehydrated with anhydrous magnesium sulfate dehydration, got the finished product
4-iodobenzaldehyde 605.52g, yield of 87%.
Embodiment 2
Organic synthesis intermediates 4-iodobenzaldehyde synthesis method, comprises the following steps:
A: 3mol 2-amino-4-iodine benzyl alcohol, 1.8L sodium sulfate solution with a
2018100826 19 Jun 2018 mass fraction of 12% were added to the reaction vessel, controlled the temperature of the solution to 24°C, controlled the stirring speed at 230 rpm, reacted for 100 min, added 700ml ethyl butyl ether solution with a mass fraction of 25%, continued to react for 1.6h;
B: added 4mol 1,4-amyl lactone solution with a mass fraction of 42%, added
3.5mol palladium nitrate powder in four times, when finished raising the temperature of the solution to 33 °C, controlled the stirring speed at 340rpm, back-flow, reacted for lOOmin, reduced the temperature of the solution to 6 °C,added 800ml potassium nitrate solution with a mass fraction of 18%, set aside 2.5h, stratified solution, separated reservoir, washed with the sodium bromide solution with a mass fraction of 14%, washed with the N-ethyl acetamide solution with a mass fraction of 45%, re-crystallized in the 2-ethanolamine solution with a mass fraction of 83%, dehydrated with activated alumina dehydration, got the finished product 4-iodobenzaldehyde 633.36g, yield of 91%.
Embodiment 3
Organic synthesis intermediates 4-iodobenzaldehyde synthesis method, comprises the following steps:
A: 3mol 2-amino-4-iodine benzyl alcohol, 1.8L sodium sulfate solution with a mass fraction of 15% were added to the reaction vessel, controlled the temperature of the solution to 26°C, controlled the stirring speed at 240 rpm, reacted for 110 min, added 700ml ethyl butyl ether solution with a mass fraction of 26%, continued to react for 2h;
B: added 5mol 1,4-amyl lactone solution with a mass fraction of 45%, added
4mol palladium nitrate powder in five times, when finished raising the temperature of the solution to 35°C, controlled the stirring speed at 350rpm, back-flow, reacted for llOmin, reduced the temperature of the solution to 9 °C,added 800ml potassium nitrate solution with a mass fraction of 22%, set aside 3h, stratified solution, separated reservoir, washed with the sodium bromide solution with a mass fraction of 16%, washed with the N-ethyl acetamide solution with a mass fraction of 47%,
2018100826 19 Jun 2018 re-crystallized in the 2-ethanolamine solution with a mass fraction of 85%, dehydrated with anhydrous calcium chloride dehydration, got the finished product 4-iodobenzaldehyde 654.24g, yield of 94%.
Infrared analysis of finished product 4-iodobenzaldehyde, infrared spectrum is 5 shown in figure 1, the analysis of data is shown in Table 1:
Table 1 Peak data
Serial Peak position Transmittance Half width Peak difference
number (cm'1) (%) (cm'1) (%)
1 806 9 18 51
2 825 23 14 19
3 834 27 9 23
4 1005 42 16 47
5 1049 47 12 45
6 1090 66 15 14
7 1160 39 17 43
8 1203 35 18 50
9 1275 46 22 16
10 1291 49 25 12
11 1380 29 24 43
12 1402 62 33 9
13 1474 61 62 12
14 1566 35 45 8
15 1585 29 23 26
16 1660 34 46 9
17 1695 30 49 22
2018100826 19 Jun 2018
18 1912 64 72 14
19 2706 50 509 6
20 2806 44 136 16
The embodiments of the present invention are merely preferred embodiments of the present invention, but the range of the present invention is not limited this, and any person who is familiar with those skilled in the arts, within the technical range of the present invention. It is intended that the technical solution and its inventive concept be replaced or modified equivalently with reference to the range of the invention.
2018100826 19 Jun 2018

Claims (4)

  1. Claims
    1. Organic synthesis intermediates 4-iodobenzaldehyde synthesis method, comprises the following steps:
    5 A: 2-amino-4-iodine benzyl alcohol, 1.8 L sodium sulfate solution were added to the reaction vessel, controlled the temperature of the solution to 20-26 °C, controlled the stirring speed at 210-240 rpm, reacted for 80-llOmin,added 700ml ethyl butyl ether solution, continued to react for l-2h;
    B: added 1,4-amyl lactone solution, added palladium nitrate powder in batch, 10 when finished raising the temperature of the solution to 30-35°C, controlled the stirring speed at 310-350rpm, back-flow, reacted for 90-110 min, reduced the temperature of the solution to 5-9 °C,added 800ml potassium nitrate solution, set aside 2-3h, stratified solution, separated reservoir, washed with the sodium bromide solution, washed with the n-ethyl acetamide solution, re-crystallized in the
    15 2-ethanolamine solution, dehydrated with dehydration, got the finished product 4- io dobenzaldehyde.
  2. 2. Organic synthesis intermediates 4-iodobenzaldehyde synthesis method according to claim 1 wherein the sodium sulfate solution has a mass fraction of
    10-15%.
    20
  3. 3. Organic synthesis intermediates 4-iodobenzaldehyde synthesis method according to claim 1 wherein the mass fraction of the ethyl butyl ether solution is
    20-26%.
  4. 4. Organic synthesis intermediates 4-iodobenzaldehyde synthesis method according to claim 1 wherein the 1, 4-amyl lactone solution has a mass fraction of
    25 40-45%.
    2018100826 19 Jun 2018
    1/1
    Figure 1
AU2018100826A 2017-09-27 2018-06-19 Organic synthesis intermediates 4-iodobenzaldehyde synthesis method Ceased AU2018100826A4 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN2017108911961 2017-09-27
CN201710891196.1A CN108238863A (en) 2017-09-27 2017-09-27 The synthetic method of organic synthesis intermediate 4- benzaldehyde iodines

Publications (1)

Publication Number Publication Date
AU2018100826A4 true AU2018100826A4 (en) 2018-08-02

Family

ID=62700339

Family Applications (1)

Application Number Title Priority Date Filing Date
AU2018100826A Ceased AU2018100826A4 (en) 2017-09-27 2018-06-19 Organic synthesis intermediates 4-iodobenzaldehyde synthesis method

Country Status (2)

Country Link
CN (1) CN108238863A (en)
AU (1) AU2018100826A4 (en)

Also Published As

Publication number Publication date
CN108238863A (en) 2018-07-03

Similar Documents

Publication Publication Date Title
CN101456855B (en) Method for preparing 1,3-propanesultone
CN104610254A (en) Low-cost preparation method for palbociclib
AU2018100826A4 (en) Organic synthesis intermediates 4-iodobenzaldehyde synthesis method
CN104926736A (en) Synthesis methods for azoxystrobin and intermediate thereof
CN106563488B (en) Titanium dioxide microballoon sphere@total silicon Silica-1 molecular sieve nucleocapsid catalyst, Preparation method and use
AU2018100827A4 (en) Drug intermediates 4-benzyloxy-3-methoxy-4'-methylbenzophenone synthesis method
CN209801245U (en) Explosion-proof lighting device is used in modified starch production
AU2018100822A4 (en) Antitumor drug intermediates 3, 5-tert-butyl-4-hydroxy benzoic acid synthesis method
AU2018100825A4 (en) Trimethoprim drug intermediate p-nitrobenzene formaldehyde synthesis method
CN105646555A (en) Terephthalic acid derivative cadmium complex and preparation method thereof
AU2018100824A4 (en) Nitro-cotton intermediates butyl butyrate synthesis method
JPS56104890A (en) Preparation of organosilane
AU2018100823A4 (en) Drug intermediates 3-ene hexenoic acid synthesis method
AU2018100820A4 (en) Pharmaceutical intermediates androstane-2,3-break-17-ketone-2, 3-dicarboxylic acid synthesis method
AU2018101125A4 (en) Drug intermediates 3,5-dimethoxybenzaldehyde synthesis method
Shizuri et al. The synthesis of a tricyclic hydroazulenone from exo-epoxygermacrene-Din connection with periplanone A
AU2018100832A4 (en) Drug intermediates 4-nitro-4'-ethyl amide diphenyl sulfone synthesis method
IES87005B2 (en) Flavones glycoside drug intermediates acetylene carboxylic acid synthesis method
AU2018100833A4 (en) The bleeding aromatic acid drugs intermediates p-toluic acid synthesis method
AU2018100420A4 (en) Organic synthesis raw materials valeric acid synthesis method
AU2018100394A4 (en) Drugs intermediates 2-formylcarbonylbenzoic acid synthesis method
AU2018100831A4 (en) Organic synthesis intermediates 2-tetrolaldehyde synthesis method
CN107459641B (en) A kind of preparation method of perfluoropolyether-modified allyloxy body
AU2018101145A4 (en) Dodecanoyl peroxide organic intermediates synthesis method
CN204156027U (en) The spacing edge-folding mechanism of battery case cam-type

Legal Events

Date Code Title Description
FGI Letters patent sealed or granted (innovation patent)
MK22 Patent ceased section 143a(d), or expired - non payment of renewal fee or expiry