CN106366018B - A kind of synthetic method of the bromo- 1- naphthonitrile of 4- - Google Patents
A kind of synthetic method of the bromo- 1- naphthonitrile of 4- Download PDFInfo
- Publication number
- CN106366018B CN106366018B CN201610749405.4A CN201610749405A CN106366018B CN 106366018 B CN106366018 B CN 106366018B CN 201610749405 A CN201610749405 A CN 201610749405A CN 106366018 B CN106366018 B CN 106366018B
- Authority
- CN
- China
- Prior art keywords
- bromo
- naphthaldehyde
- naphthalene
- oxime
- preparation
- 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.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/10—Preparation of halogenated hydrocarbons by replacement by halogens of hydrogen atoms
- C07C17/12—Preparation of halogenated hydrocarbons by replacement by halogens of hydrogen atoms in the ring of aromatic compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/10—Preparation of halogenated hydrocarbons by replacement by halogens of hydrogen atoms
- C07C17/14—Preparation of halogenated hydrocarbons by replacement by halogens of hydrogen atoms in the side-chain of aromatic compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C249/04—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of oximes
- C07C249/08—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of oximes by reaction of hydroxylamines with carbonyl 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
- C07C45/28—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of CHx-moieties
Abstract
The invention discloses a kind of synthetic method of the bromo- 1- naphthonitrile of 4-, the method comprises the steps of: step 1: using 1- methyl naphthalene as raw material, bromine replaces the hydrogen on 1- methyl naphthalene phenyl ring to obtain the bromo- 1- methyl naphthalene (I) of 4-；Step 2: bromine replaces the hydrogen on the methyl of the bromo- 1- methyl naphthalene (I) of 4- to obtain the bromo- 1- bromomethyl naphthalene (II) of 4-；The bromo- 1- bromomethyl naphthalene (II) of step 3:4- occurs Suo Mulai and reacts to obtain the bromo- 1- naphthaldehyde (III) of 4-；The bromo- 1- naphthaldehyde (III) of step 4:4- obtains the bromo- 1- naphthaldehyde oxime (IV) of 4- at oxime；Bromo- 1- naphthaldehyde oxime (IV) dehydration of step 5:4- obtains the bromo- 1- naphthonitrile (V) of 4-.The present invention have many advantages, such as Process Route Planning is reasonable, supplementary material is cheap and easy to get, high income, it is at low cost, be suitable for industrialized production.
Description
Technical field
The invention belongs to organic synthetic route design fields, in particular to the synthetic method of the bromo- 1- naphthonitrile of 4-.
Background technique
The bromo- 1- naphthonitrile of 4- is a kind of very important organic intermediate, seeks a kind of easy, cheap synthetic method tool
There is important meaning.
Document and patent report about the bromo- 1- naphthonitrile of 4- mainly have:
One, world patent WO2007087488A2 and tetrahedron flash report (Tetrahedron), 46 (6), 2205-2212
This method obtains the bromo- 1- naphthonitrile of 4- using the bromo- naphthalidine of 4- as raw material, by diazo-reaction, substitution reaction.
The drawbacks of this method is that the diazonium salt of generation is unstable, and has used the potassium cyanide of severe toxicity.
Two, United States Patent (USP) US20040122001A1
This method obtains the bromo- 1- naphthalene of 4- using 4- amino -1- naphthonitrile as raw material, by diazo-reaction, substitution reaction
Formonitrile HCN.The drawbacks of this method is that the diazonium salt of generation is unstable, and raw material is not cheap.
Three, Czechoslovakia's chemical communication collection (Collection of Czechoslovak Chemical
Communications), 65 (11), 1791-1804
This method using 1,2,3,4-tetrahydro-naphthalene as raw material, by substitution, cancellation, substitution reaction and obtain the bromo- 1- naphthalene of 4-
Formonitrile HCN.The drawbacks of this method is the bromine for having used severe toxicity, and final step is easy to generate side reaction and product is caused to be difficult to point
From.
Four, European Journal of Organic Chemistry (European Journal of Organic Chemistry), 2014 (19),
4115-4122
This method using the bromo- 4- methyl naphthalene of 1- as raw material, by substitution, ammonification, elimination reaction and obtain the bromo- 1- naphthalene first of 4-
Nitrile.The drawbacks of this method is to have used very malicious hydrogen bromide and ammonia.
Summary of the invention
In order to overcome the shortcomings of it is mentioned hereinbefore or there are the problem of, the purpose of the present invention is to provide a kind of no meta positions
Isomers, processing step are simple, production cost is low, finished product is with high purity and are suitable for the bromo- 1- naphthonitrile of 4- of industrialized production
Synthetic method.
According to the present invention, a kind of synthetic method of bromo- 1- naphthonitrile of 4- is provided, is synthesized by following approach:
The synthetic method comprises the steps of:
Step 1: using 1- methyl naphthalene as raw material, bromine replaces the hydrogen on 1- methyl naphthalene phenyl ring to obtain the bromo- 1- methyl naphthalene (I) of 4-；
Step 2: bromine replaces the hydrogen on the methyl of the bromo- 1- methyl naphthalene (I) of 4- to obtain the bromo- 1- bromomethyl naphthalene (II) of 4-；
The bromo- 1- bromomethyl naphthalene (II) of step 3:4- occurs Suo Mulai and reacts to obtain the bromo- 1- naphthaldehyde (III) of 4-；
The bromo- 1- naphthaldehyde (III) of step 4:4- obtains the bromo- 1- naphthaldehyde oxime (IV) of 4- at oxime；
Bromo- 1- naphthaldehyde oxime (IV) dehydration of step 5:4- obtains the bromo- 1- naphthonitrile (V) of 4-.
Wherein, bromating agent used in step 1 is N-bromosuccinimide, and solvent used is acetonitrile.
Wherein, 1- methyl naphthalene in step 1, N-bromosuccinimide mole ratio be 1:1.0~1.2, reaction temperature
It is 20~25 DEG C.
Wherein, bromating agent used in step 2 is N-bromosuccinimide, and catalyst used is benzoyl peroxide
(BPO), solvent used is carbon tetrachloride.
Wherein, the bromo- 1- methyl naphthalene (I) of 4- in step 2, N-bromosuccinimide, benzoyl peroxide (BPO) mole
For amount than being 1:0.9~1.0:0.02~0.04, reaction temperature is 70~78 DEG C.
Wherein, oxidant used in step 3 is hexamethylenetetramine, and solvent used is acetic acid and water.The bromo- 1- bromine of 4-
Methyl naphthalene (II), hexamethylenetetramine mole ratio be 1:1.5~2.5, reaction temperature be 95~105 DEG C.
Wherein, use hydroxylamine hydrochloride at oxime in step 4, alkali used is triethylamine, and solvent used is acetonitrile.
Wherein, the bromo- 1- naphthaldehyde (III) of 4- in step 4, hydroxylamine hydrochloride, triethylamine mole ratio be 1:3.0~4.5:
3.0~4.5, reaction temperature is 75~82 DEG C.
Wherein, dehydrating agent used in step 5 is copper acetate monohydrate, and solvent used is acetonitrile.
Wherein, the bromo- 1- naphthaldehyde oxime (IV) of 4- in step 5, copper acetate monohydrate mole ratio be 1:0.05~0.2, instead
Answering temperature is 75~82 DEG C.
The invention has the following advantages that present invention process highway route design is reasonable, supplementary material is cheap and easy to get, high income, cost
It is low, be suitable for industrialized production.
Specific embodiment
For above and other objects of the present invention, feature and advantage can be clearer and more comprehensible, preferred embodiment is cited below particularly,
It is described in detail below:
1, the synthesis of the bromo- 1- methyl naphthalene (I) of 4-
1- methyl naphthalene 300g, 3kg acetonitrile is added in embodiment 1:5L four-hole bottle, is cooled to 0 DEG C, 413g is added in four batches
N-bromosuccinimide (NBS), makes temperature less than 25 DEG C, adds and reacts overnight under room temperature (20~25 DEG C).Contact plate, reaction
It finishes, 25% sodium hydrogensulfite (NaHSO is added3) 120g, after stirring 0.5h, 30 DEG C are spin-dried for solvent, 800ml n-hexane is added,
Water 1200g extraction, water phase are extracted twice with n-hexane 500ml*2 again, merge organic phase, are washed with saturation NaCl solution 600g*2,
Solvent is spin-dried for for 40 DEG C after anhydrous magnesium sulfate dries, filters, and is drawn and is done to obtain bromo- 1- methyl naphthalene (I) crude product of 461.8g 4-, yield 99%.
2, the synthesis of the bromo- 1- bromomethyl naphthalene (II) of 4-
The bromo- 1- methyl naphthalene (I) of 461.8g 4-, 7.2kg carbon tetrachloride, 375.6g N- are added in embodiment 2:5L four-hole bottle
Bromosuccinimide, 20.5g BPO are warming up to 70~78 DEG C (preferably 77 DEG C) reactions and are refluxed overnight.Contact plate has been reacted
Finish.It is cooled to room temperature, is filtered, 40 DEG C are spin-dried for solvent.Ethyl alcohol 1200g is added, is warming up to 70 DEG C of guarantor 1h, is cooled to room temperature, filters,
Filter cake is washed with ethyl alcohol, and after draining, 35 DEG C of dry bromo- 1- bromomethyl naphthalenes (II) of 500g 4-, two step yields 79% are (with 1- methyl
Naphthalene is counted).
3, the synthesis of the bromo- 1- naphthaldehyde (III) of 4-
Be added in embodiment 3:3L there-necked flask the bromo- 1- bromomethyl naphthalene (II) of 318g 4-, 222.9g hexamethylenetetramine,
795g glacial acetic acid, 795g water, 95 DEG C of back flow reaction 3h, contact plate, end of reaction, fast drop 636g concentrated hydrochloric acid drip off reflux
0.5h.It is cooled to room temperature, 4L water is added, stirs 3h.Filtering, filter cake use 2L water to be beaten 2h again, filter, and filter cake is washed with water twice,
It drains, 40 DEG C of drying.318g ethyl alcohol recrystallization, dry the bromo- 1- naphthaldehyde (III) of 177.9g 4-, yield 71.3% is added.Its
The mole ratio of the middle bromo- 1- bromomethyl naphthalene (II) of 4- and hexamethylenetetramine is 1:1.5.
The bromo- 1- bromomethyl naphthalene (II) of 318g 4-, 297g hexamethylenetetramine, 795g are added in embodiment 4:3L there-necked flask
Glacial acetic acid, 795g water, 105 DEG C of back flow reaction 3h, contact plate, end of reaction, fast drop 636g concentrated hydrochloric acid drip off reflux 0.5h.
It is cooled to room temperature, 4L water is added, stirs 3h.Filtering, filter cake use 2L water to be beaten 2h again, filter, and filter cake is washed with water twice, drains,
40 DEG C of drying.318g ethyl alcohol recrystallization, dry the bromo- 1- naphthaldehyde (III) of 200g 4-, yield 80% is added.The wherein bromo- 1- of 4-
The mole ratio of bromomethyl naphthalene (II) and hexamethylenetetramine is 1:2,
Be added in embodiment 5:3L there-necked flask the bromo- 1- bromomethyl naphthalene (II) of 318g 4-, 371.5g hexamethylenetetramine,
795g glacial acetic acid, 795g water, 100 DEG C of back flow reaction 3h, contact plate, end of reaction, fast drop 636g concentrated hydrochloric acid drip off reflux
0.5h.It is cooled to room temperature, 4L water is added, stirs 3h.Filtering, filter cake use 2L water to be beaten 2h again, filter, and filter cake is washed with water twice,
It drains, 40 DEG C of drying.318g ethyl alcohol recrystallization, dry the bromo- 1- naphthaldehyde (III) of 200.4g 4-, yield 80.4% is added.Its
The mole ratio of the middle bromo- 1- bromomethyl naphthalene (II) of 4- and hexamethylenetetramine is 1:2.5,
4, the synthesis of the bromo- 1- naphthaldehyde oxime (IV) of 4-
The bromo- 1- naphthaldehyde (III) of 133g 4-, 157g hydroxylamine hydrochloride, 1kg acetonitrile, stirring are added in embodiment 6:3L there-necked flask
Lower dropwise addition 229g triethylamine.79 DEG C of reaction 3h, contact plate, end of reaction.It is cooled to room temperature, decompression evaporates 500g acetonitrile, adds
1500g water, EA1000g, extraction, water phase use 400g EA to extract again, merge organic phase, are washed with saturation NaCl solution 1000g, member
Bright powder is dried overnight, and is drawn and is done to obtain bromo- 1- naphthaldehyde oxime (IV) the crude product 141g of 4-, yield 99.6%.Wherein, the bromo- 1- naphthaldehyde of 4-
(III), hydroxylamine hydrochloride, triethylamine mole ratio be 1:4:4,
The bromo- 1- naphthaldehyde (III) of 133g 4-, 118g hydroxylamine hydrochloride, 1kg acetonitrile, stirring are added in embodiment 7:3L there-necked flask
Lower dropwise addition 257.6g triethylamine.75 DEG C of reaction 3h, contact plate, end of reaction.It is cooled to room temperature, depressurizes and evaporates 500g acetonitrile, then plus
Entering 1500g water, EA1000g is extracted, and water phase uses 400g EA to extract again, merges organic phase, it is washed with saturation NaCl solution 1000g,
Anhydrous sodium sulphate is dried overnight, and is drawn and is done to obtain bromo- 1- naphthaldehyde oxime (IV) the crude product 130g of 4-, yield 91.9%.Wherein, the bromo- 1- naphthaldehyde of 4-
(III), hydroxylamine hydrochloride, triethylamine mole ratio be 1:3.0:4.5.
The bromo- 1- naphthaldehyde (III) of 133g 4-, 176.9g hydroxylamine hydrochloride, 1kg acetonitrile are added in embodiment 8:3L there-necked flask, stirs
Mix lower dropwise addition 171.7g triethylamine.82 DEG C of reaction 3h, contact plate, end of reaction.It is cooled to room temperature, decompression evaporates 500g acetonitrile, then
1500g water is added, EA1000g, extraction, water phase uses 400g EA to extract again, merges organic phase, with saturation NaCl solution 1000g
It washes, anhydrous sodium sulphate is dried overnight, and is drawn and is done to obtain bromo- 1- naphthaldehyde oxime (IV) the crude product 124.9g of 4-, yield 88.3%.Wherein, the bromo- 1- naphthalene of 4-
Aldehyde (III), hydroxylamine hydrochloride, triethylamine mole ratio be 1:4.5:3.0.
5, the synthesis of the bromo- 1- naphthonitrile (V) of 4-
Be added in embodiment 9:3L there-necked flask the crude product 141g of the bromo- 1- naphthaldehyde oxime (IV) of 4-, copper acetate monohydrate 11.3g,
1137g acetonitrile, 79 DEG C of reactions are refluxed overnight, contact plate, end of reaction.It is cooled to room temperature, decompression evaporates 600g acetonitrile, adds
1500g water, methylene chloride 1000g, extraction, water phase use 500g*2 methylene chloride to extract again, merge organic phase, molten with saturation NaCl
Liquid 1500g is washed, and anhydrous sodium sulphate stirring is dried overnight.Filtering, 40 DEG C of filtrate are spin-dried for solvent, cross short column, and methylene chloride makees eluant, eluent, draw
It is dry that bromo- 1- naphthonitrile (V) 124g of 4-, two step total recoverys are 94.6% (in terms of the bromo- 1- naphthaldehyde of 4-), liquid phase purity 99.3%.
Wherein, the mole ratio of the bromo- 1- naphthaldehyde oxime (IV) of 4- and copper acetate monohydrate is 1:0.1.
Be added in embodiment 10:3L there-necked flask the crude product 141g of the bromo- 1- naphthaldehyde oxime (IV) of 4-, copper acetate monohydrate 5.6g,
1137g acetonitrile, 75 DEG C of reactions are refluxed overnight, contact plate, end of reaction.It is cooled to room temperature, decompression evaporates 600g acetonitrile, adds
1500g water, methylene chloride 1000g, extraction, water phase use 500g*2 methylene chloride to extract again, merge organic phase, molten with saturation NaCl
Liquid 1500g is washed, and anhydrous sodium sulphate stirring is dried overnight.Filtering, 40 DEG C of filtrate are spin-dried for solvent, cross short column, and methylene chloride makees eluant, eluent, draw
It is dry that bromo- 1- naphthonitrile (V) 109g of 4-, two step total recoverys are 83% (in terms of the bromo- 1- naphthaldehyde of 4-), liquid phase purity 98.5%.Its
In, the mole ratio of the bromo- 1- naphthaldehyde oxime (IV) of 4- and copper acetate monohydrate is 1:0.05.
Be added in embodiment 11:3L there-necked flask the crude product 141g of the bromo- 1- naphthaldehyde oxime (IV) of 4-, copper acetate monohydrate 14g,
1137g acetonitrile, 82 DEG C of reactions are refluxed overnight, contact plate, end of reaction.It is cooled to room temperature, decompression evaporates 600g acetonitrile, adds
1500g water, methylene chloride 1000g, extraction, water phase use 500g*2 methylene chloride to extract again, merge organic phase, molten with saturation NaCl
Liquid 1500g is washed, and anhydrous sodium sulphate stirring is dried overnight.Filtering, 40 DEG C of filtrate are spin-dried for solvent, cross short column, and methylene chloride makees eluant, eluent, draw
It is dry that bromo- 1- naphthonitrile (V) 124.3g of 4-, two step total recoverys are 94.7% (in terms of the bromo- 1- naphthaldehyde of 4-), liquid phase purity
99.3%.Wherein, the mole ratio of the bromo- 1- naphthaldehyde oxime (IV) of 4- and copper acetate monohydrate is 1:0.125.
Be added in embodiment 12:3L there-necked flask the crude product 141g of the bromo- 1- naphthaldehyde oxime (IV) of 4-, copper acetate monohydrate 22.6g,
1137g acetonitrile, 79 DEG C of reactions are refluxed overnight, contact plate, end of reaction.It is cooled to room temperature, decompression evaporates 600g acetonitrile, adds
1500g water, methylene chloride 1000g, extraction, water phase use 500g*2 methylene chloride to extract again, merge organic phase, molten with saturation NaCl
Liquid 1500g is washed, and anhydrous sodium sulphate stirring is dried overnight.Filtering, 40 DEG C of filtrate are spin-dried for solvent, cross short column, and methylene chloride makees eluant, eluent, draw
It is dry that bromo- 1- naphthonitrile (V) 124.3g of 4-, two step total recoverys are 94.7% (in terms of the bromo- 1- naphthaldehyde of 4-), liquid phase purity
99.3%.Wherein, the mole ratio of the bromo- 1- naphthaldehyde oxime (IV) of 4- and copper acetate monohydrate is 1:0.2.
Although the present invention has been disclosed in the preferred embodiments as above, however, it is not to limit the invention, any affiliated technology
The technical staff in field, without departing from the spirit and scope of the present invention, when can make a little change and improve, therefore the present invention
Protection scope when view as defined in claim subject to.
Claims (9)
1. a kind of synthetic method of the bromo- 1- naphthonitrile of 4-, which is characterized in that synthesized by following approach:
The synthetic method comprises the steps of:
Step 1: using 1- methyl naphthalene as raw material, bromine replaces the hydrogen on 1- methyl naphthalene phenyl ring to obtain the bromo- 1- methyl naphthalene (I) of 4-；
Step 2: bromine replaces the hydrogen on the methyl of the bromo- 1- methyl naphthalene (I) of 4- to obtain the bromo- 1- bromomethyl naphthalene (II) of 4-；
The bromo- 1- bromomethyl naphthalene (II) of step 3:4- occurs Suo Mulai and reacts to obtain the bromo- 1- naphthaldehyde (III) of 4-；
The bromo- 1- naphthaldehyde (III) of step 4:4- obtains the bromo- 1- naphthaldehyde oxime (IV) of 4- at oxime；
Bromo- 1- naphthaldehyde oxime (IV) dehydration of step 5:4- obtains the bromo- 1- naphthonitrile (V) of 4-,
Oxidant used in step 3 be hexamethylenetetramine, solvent used be acetic acid and water,
Using hydroxylamine hydrochloride at oxime in step 4, alkali used is triethylamine, and solvent used is acetonitrile.
2. synthetic method according to claim 1, which is characterized in that bromating agent used in step 1 is N- bromo amber
Acid imide, solvent used are acetonitrile.
3. preparation method according to claim 2, which is characterized in that 1- methyl naphthalene, N-bromosuccinimide in step 1
Mole ratio be 1:1.0~1.2, reaction temperature be 20~25 DEG C.
4. preparation method according to claim 1, which is characterized in that bromating agent used in step 2 is N- bromo amber
Acid imide, catalyst used are benzoyl peroxide (BPO), and solvent used is carbon tetrachloride.
5. the preparation method according to claim 4, which is characterized in that the bromo- 1- methyl naphthalene (I) of 4-, N- bromo amber in step 2
Amber acid imide, benzoyl peroxide (BPO) mole ratio be 1:0.9~1.0:0.02~0.04, reaction temperature be 70~78
℃。
6. preparation method according to claim 1, which is characterized in that the bromo- 1- bromomethyl naphthalene (II) of 4-, hexamethylenetetramine
Mole ratio be 1:1.5~2.5, reaction temperature be 95~105 DEG C.
7. preparation method according to claim 1, which is characterized in that the bromo- 1- naphthaldehyde (III) of 4-, hydrochloric acid hydroxyl in step 4
Amine, triethylamine mole ratio be 1:3.0~4.5:3.0~4.5, reaction temperature be 75~82 DEG C.
8. preparation method according to claim 1, which is characterized in that dehydrating agent used in step 5 is a hydration acetic acid
Copper, solvent used are acetonitrile.
9. preparation method according to claim 1, which is characterized in that the bromo- 1- naphthaldehyde oxime (IV) of 4-, a hydration in step 5
The mole ratio of copper acetate is 1:0.05~0.2, and reaction temperature is 75~82 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610749405.4A CN106366018B (en) | 2016-08-29 | 2016-08-29 | A kind of synthetic method of the bromo- 1- naphthonitrile of 4- |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610749405.4A CN106366018B (en) | 2016-08-29 | 2016-08-29 | A kind of synthetic method of the bromo- 1- naphthonitrile of 4- |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106366018A CN106366018A (en) | 2017-02-01 |
| CN106366018B true CN106366018B (en) | 2019-07-23 |
Family
ID=57903607
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610749405.4A Active CN106366018B (en) | 2016-08-29 | 2016-08-29 | A kind of synthetic method of the bromo- 1- naphthonitrile of 4- |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106366018B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111100132A (en) * | 2019-12-31 | 2020-05-05 | 厦门本素药业有限公司 | Method for synthesizing procarbazine hydrochloride intermediate |
| CN113979871B (en) * | 2021-11-30 | 2023-11-10 | 江苏同禾药业有限公司 | Preparation method of N-methyl-1-naphthylmethylamine and intermediate N-methyl-1-naphthylmethylamine |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI412322B (en) * | 2005-12-30 | 2013-10-21 | Du Pont | Isoxazolines for controlling invertebrate pests |
| WO2010079077A1 (en) * | 2008-12-18 | 2010-07-15 | Novartis Ag | Isoxazolines derivatives and their use as pesticide |
| TW201437200A (en) * | 2013-01-15 | 2014-10-01 | Intermune Inc | Lysophosphatidic acid receptor antagonists |
-
2016
- 2016-08-29 CN CN201610749405.4A patent/CN106366018B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN106366018A (en) | 2017-02-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2020147861A1 (en) | Electrochemical preparation method for β-trifluoromethylamide compound | |
| CN101137647A (en) | Synthesis of himbacine analogs | |
| CN106366018B (en) | A kind of synthetic method of the bromo- 1- naphthonitrile of 4- | |
| CN103724329A (en) | Preparation method of 4-[5-(pyridyl-4-yl)-1H-[1,2,4]triazolyl-3-yl]pyridyl-2-formonitrile | |
| CN109956906A (en) | A kind of preparation method for disliking La Geli key intermediate | |
| CN103896855B (en) | The synthetic method of the fluoro-6-chlorine of a kind of 4-(1-bromoethyl)-5-pyrimidine | |
| CN105001031B (en) | Ionic iron (III) coordination compound containing single phenol functionalization Imidazole cation and preparation method and application | |
| CN109575014A (en) | Benzimidazole simultaneously [2,1-a] isoquinolinone compound and preparation method thereof | |
| CN110698416A (en) | Preparation method of pyridine quinazoline intermediate | |
| CN105820145B (en) | A kind of preparation method of 5- nitryl furfural and Nifuratel | |
| CN113336764B (en) | Bipyridine ligand with axial chirality and synthetic method thereof | |
| CN113501777B (en) | Synthetic method of indoline-5-ylmethylamine dihydrochloride | |
| CN103554041B (en) | A kind of synthesis technique preparing Anastrozole | |
| CN103755657B (en) | A kind of preparation method of Rivaroxaban intermediate | |
| CN101845062B (en) | Method for preparing biferrocenyl chalcone | |
| CN102382053B (en) | A kind of method preparing tolvaptan intermediate | |
| KR100677838B1 (en) | Process for the preparation of alicyclic ketone and alkyl-substituted alicyclic ester | |
| CN106083631B (en) | A kind of preparation method of equal amido phenenyl acid | |
| CN108358866A (en) | A kind of preparation method of Febustat intermediate and its application in preparing Febustat | |
| CN113354623B (en) | Preparation method of ilaprazole key intermediate 5- (1H-pyrrole-1-yl) -2-mercaptobenzimidazole | |
| CN114380835B (en) | Preparation method of 7- (3,4-dimethoxyphenyl) -2-pyrazole [1,5-A ] pyrimidine carboxylic acid | |
| CN102079720A (en) | Method for preparing 1-benzylpiperidine-4-carboxaldehyde | |
| CN107602477A (en) | A kind of process for purification of cyazofamid active compound | |
| CN112724089B (en) | Synthesis process of 2-amino-3-bromo-6-chloropyrazine | |
| CN107663151B (en) | Intermediate synthesis method of flumatinib mesylate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |