CN1060462C - Method for prepn. of a, a'-fluorohalogenated xylene - Google Patents

Method for prepn. of a, a'-fluorohalogenated xylene Download PDF

Info

Publication number
CN1060462C
CN1060462C CN97106790A CN97106790A CN1060462C CN 1060462 C CN1060462 C CN 1060462C CN 97106790 A CN97106790 A CN 97106790A CN 97106790 A CN97106790 A CN 97106790A CN 1060462 C CN1060462 C CN 1060462C
Authority
CN
China
Prior art keywords
fluoride
fluorine
halogen substituted
class
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.)
Expired - Fee Related
Application number
CN97106790A
Other languages
Chinese (zh)
Other versions
CN1184799A (en
Inventor
茅云宇
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.)
Shanghai Institute of Organic Chemistry of CAS
Original Assignee
Shanghai Institute of Organic Chemistry of CAS
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 Shanghai Institute of Organic Chemistry of CAS filed Critical Shanghai Institute of Organic Chemistry of CAS
Priority to CN97106790A priority Critical patent/CN1060462C/en
Publication of CN1184799A publication Critical patent/CN1184799A/en
Application granted granted Critical
Publication of CN1060462C publication Critical patent/CN1060462C/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Classifications

    • 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
    • C07C17/20—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms
    • C07C17/202—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction
    • C07C17/206—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction the other compound being HX
    • 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
    • C07C17/20—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms
    • C07C17/202—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction
    • C07C17/208—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction the other compound being MX

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The present invention relates to a method for preparing alpha, alpha'-fluorine halogen substituted xylene, namely that a corresponding ortho or para product disclosed in the following formula (X is equal to Br or Cl) is synthesized from an ortho position or a para position disclosed in the top right formula (X is equal to Br or Cl) as raw materials in solvent or no solvent at 40 to 220 DEG C and normal pressure of-30 atm under the conditions of a catalyst or no catalyst in the mode of fluorine hydride or fluorine negative ion reagents, such as sodium fluoride, potassium fluoride, cesium fluoride, sodium fluoride-calcium fluoride, potassium fluoride-calcium fluoride, cesium fluoride-calcium fluoride, etc., as fluorination reagents. The method has the advantages of short synthetic route, high yield, short reaction time and low price and easy acquirement of the raw materials, is suitable for large-scale production and has wide application prospects on industry.

Description

α, the preparation method of α '-fluorine halogen substituted dimethyl benzene
The present invention relates to prepare a class α, the method for α '-fluorine halogen substituted dimethyl benzene.
Compound α, α '-fluorine halogen substituted dimethyl benzene Intermediate as a kind of organic synthesis is widely used at organic synthesis and application facet, Chow, S.W.Patent US3297519; Chow, S.W.; Pilato, L.A.; Wheelwright, W.L.J.Org.Chem.1970,35,20; William R.Dolbier, Jr; Mohammed AliAsghar; He-Qi Pan Patent US5210341; WilliamR.Dolbier, Jr; Mohammed Ali Asghar; He-Qi Pan; And LechCelewicz J.Org.Chem.1993,58, reported all among the 1827-1830 that it can be used for preparing fluoro-containing macromolecule material, potential using value aspect preparation fluorine-containing medicines and agricultural chemicals.Hasek, W.R.; Smith, W.C.; Engelhardt, V.A.; J.Am.Chem.Soc.1960,82,543 and Fuqua, S.A.; Parkhurst, R.F.M.; Silverstein, R.M.; Tetrahedron 1964,20, reported in 1625. relevant synthetic The method of (X=Br or Cl) is being raw material to two phenyl aldehydes, fluoridizes bromination with sulfur tetrafluoride earlier or chlorination makes product again.That is: , the report of the synthetic method of ortho position product is not arranged at present as yet, but, is difficult to adapt to industrial production because above-mentioned synthetic method raw material, reaction reagent and reaction conditions and the equal more complicated of step and productive rate are low.Therefore chemist is being sought a synthetic method that synthetic route is short, productive rate is high always.
The object of the invention just provides the synthetic method that a kind of energy is fit to scale operation.The present invention is achieved by the following scheme, promptly with ortho position or contraposition
Figure 9710679000041
Be raw material, wherein X=Br or Cl, under the condition of catalyzer or catalyst-free, solvent or solvent-free in, under normal pressure-30atm pressure condition, with fluorination reagent at 40-220 ℃ of 0.5-30 hour synthetic corresponding ortho position of reaction or contraposition product down:
Figure 9710679000042
Wherein X=Br or Cl; Reaction formula is as follows:
Figure 9710679000043
(1) fluorination reagent
(2) catalyzer or catalyst-free
(3) solvent or solvent-free
(4) normal pressure-30atm wherein chlorination reagent be hydrogen fluoride or fluorine anion reagent, wherein fluorine anion reagent is Sodium Fluoride, Potassium monofluoride, cesium fluoride, Sodium Fluoride-Calcium Fluoride (Fluorspan), Potassium monofluoride-Calcium Fluoride (Fluorspan), cesium fluoride-Calcium Fluoride (Fluorspan); Used catalyzer is SbCl 5, 18 the hat-6, R fSO 2F, wherein Rf=C nF 2n+1, n=2-12; Solvent is Skellysolve A, normal hexane, hexanaphthene, sherwood oil, methylene dichloride, trichloromethane, tetracol phenixin, tetrahydrofuran (THF), ether, benzene,toluene,xylene, pyridine, triethylamine, fluorochlorohydrocarbon and surrogate thereof; The recommendation response condition is under catalyzer and solvent condition, and reaction pressure is 10-20atm; Temperature of reaction is 70-120 ℃; Reaction times is 3-6 hour.
Concrete experimental procedure is with raw material-ortho position or contraposition
Figure 9710679000051
Drop in the reactor, add solvent and solubilizing agent not, add catalyzer or do not add catalyzer, react with fluorination reagent, carry out if be reflected in the autoclave, and be fluorination reagent, after dropping into raw material, fasten autoclave and vacuumize with HF, add fluorination reagent after being cooled to-60 ℃ with dry ice/acetone batch, rise to the reaction of room temperature post-heating again; Carry out if be reflected in the normal pressure still, when being fluorination reagent with HF, HF needs to add gradually in reaction process; Temperature of reaction remains on 40-220 ℃ proper temperature according to the difference of reaction conditions, reacts 0.5-30 hour, after reaction finishes, and purification processes, distillation and obtain product.
For existing technology, reactions steps is a single step reaction to this method aspect preparation, and synthetic route is short, and easy and simple to handle, raw material cheaply is easy to get and the productive rate height, is suitable for large-scale commercial production.
Following examples help to understand the present invention, but are not limited to content of the present invention
Embodiment 1
Raw material Drop in 21 autoclaves, fasten autoclave and vacuumize, autoclave is cooled to-60 ℃, add SbCl by the gas phase pipe with dry ice/acetone batch 5And HF, autoclave leaves dry ice/acetone batch, rise to room temperature after, the beginning reacting by heating, after a few hours, stop the heating, reduce to room temperature after, emit by product HBr and a small amount of unreacted HF from the gas phase pipe, tail gas absorbs with alkali lye.Under the ventilation situation, open autoclave, slowly add entry; Behind the decomposition catalyst, reaction mixture divides oil-yielding stratum with separating funnel, and after oil reservoir is used sig water and water washing secondary, but underpressure distillation gets
Figure 9710679000061
, actual conditions and result are as follows:
Raw material (g) HF (g) SbCl 5(g) Temperature of reaction (℃) Reaction times (hour) Pressure (atm) Productive rate %
?200 ?30 ?10 ?40 ?4 ?3．2 ?1．3
?200 ?30 ?10 ?60 ?4 ?4．7 ?15
?200 ?30 ?10 ?80 ?4 ?7．3 ?43
?200 ?30 ?10 ?100 ?4 ?10．5 ?63
?200 ?30 ?10 ?120 ?4 ?16．2 ?27
?200 ?30 ?10 ?140 ?4 ?23．7 ?6．2
mp：107-110℃／25mmHg；
1HNMRδ：7．34-7．92；
19FNMR δ: φ-45.03ppm (s); Ultimate analysis C 8H 4Br 2F 4:
Calculated value: C:28.60; H:1.20; Br:47.57, F:22.62;
Measured value: C:28.49; H:1.08; Br:47.70, F:22.54.
Embodiment 2
Raw material Drop in 21 autoclaves, fasten autoclave and vacuumize, autoclave is cooled to-60 ℃, add HF by the gas phase pipe with dry ice/acetone batch, autoclave leaves dry ice/acetone batch, after rising to room temperature, the beginning reacting by heating is after a few hours, stop heating, after reducing to room temperature, emit by product HBr and a small amount of unreacted HF from the gas phase pipe, tail gas absorbs with alkali lye.Reaction mixture is told oily matter with separating funnel, use sig water and water washing, drying, but underpressure distillation gets , actual conditions and result are as follows:
Raw material HF Reaction temperature Reaction times Pressure Productive rate %
(g) ?(g ?) Degree (℃) (hour) (atm)
?200 ?30 ?40 ?10 ?2．9 ?0．8
?200 ?30 ?60 ?10 ?4．3 ?1．6
?200 ?30 ?80 ?10 ?6．9 ?12
?200 ?30 ?100 ?10 ?9．6 ?27
?200 ?30 ?120 ?10 ?15．3 ?8
?200 ?30 ?140 ?10 ?21．8 ?4．3
mp：109-112℃／28mmHg；
1HNMRδ：7．69ppm(s)；
19FNMR δ: φ-45.65ppm (s); Ultimate analysis C 8H 4Br 2F 4:
Calculated value: C:28.60; H:1.20; Br:47.57 F:22.62
Measured value: C:28.54; H:1.15; Br:47.66 F:22.59
Embodiment 3
Raw material Drop in 21 autoclaves, pour solvent again into, fasten autoclave, autoclave is cooled to-60 ℃ with dry ice/acetone batch, vacuumizes again, add HF by the gas phase pipe, autoclave leaves dry ice/acetone batch, after rising to room temperature, the beginning reacting by heating is after a few hours, stop heating, after reducing to room temperature, emit by product HCl and a small amount of unreacted HF, sig water can be added with remaining HCl and the HF of neutralizing from liquid-phase tube from the gas phase pipe.Open autoclave under the ventilation situation, take out reaction mixture and tell organic phase, organic phase washes the secondary after drying with water, and air distillation removes and desolvates, and underpressure distillation gets again , actual conditions and result are as follows:
Raw material HF Solvent (ml) Reaction temperature Reaction times Pressure Productive rate
(g) (g ) Degree (℃) (hour) (atm) ％
200 ?30 Skellysolve A 60 ?30 ?30 ?39
200 ?30 Normal hexane 70 ?25 ?26．1 ?59
200 ?30 Hexanaphthene 90 ?6 ?17．2 ?44
?200 ?60 Sherwood oil 80 ?20 ?15．7 ?43
?200 ?60 Methylene dichloride 70 ?18 ?20．1 ?51
?200 ?90 Trichloromethane 100 ?5 ?16．2 ?53
?200 ?90 Tetracol phenixin 90 ?6 ?14．2 ?37
?200 ?100 Tetrahydrofuran (THF) 90 ?4 ?7．1 ?17
?200 ?100 Ether 60 ?15 ?22．3 ?14
?200 ?100 Benzene 110 ?3 ?15．1 ?37
?200 ?100 Toluene 130 ?3 ?13．2 ?26
?200 ?120 Dimethylbenzene 140 ?2 ?6．2 ?23
?200 ?120 Pyridine 100 ?6 ?12．1 ?9
?200 ?150 Triethylamine 100 ?6 ?8．7 ?5
?200 ?150 Fluorochlorohydrocarbon 220 ?0．5 ?15．7 ?47
mp：68-70℃／18mmHg；
1NMRδ：7．50-7．97ppm(s)；
19FNMR δ: φ-45.03ppm (s); Ultimate analysis C 8H 4Cl 2F 4:
Calculated value: C:38.90; H:1.63; Cl:28.70; F:30.76.
Measured value: C:38.85; H:1.59; Cl:28.75; F:30.80.
Embodiment 4
Raw material
Figure 9710679000081
Drop in 21 autoclaves, pour normal hexane again into, fasten autoclave, autoclave is cooled to-60 ℃ with dry ice/acetone batch, vacuumizes again, add HF by the gas phase pipe, autoclave leaves dry ice/acetone batch, after rising to room temperature, the beginning reacting by heating is after a few hours, stop heating, after reducing to room temperature, emit by product HCl and a small amount of unreacted HF, sig water can be added with remaining HCl and the HF of neutralizing from liquid-phase tube from the gas phase pipe.Open autoclave under the ventilation situation, take out reaction mixture and tell organic phase, organic phase washes the secondary after drying with water, and air distillation removes and desolvates, and underpressure distillation gets again , actual conditions and result are as follows:
Raw material (g) HF(g) Normal hexane (ml) Temperature of reaction (℃) Reaction times (hour) Pressure (atm) Productive rate %
200 ?30 ?1000 ?100 ?1 ?14．0 ?30
?200 ?30 ?1000 ?100 ?2 ?15．3 ?40
?200 ?30 ?1000 ?100 ?3 ?16．0 ?53
?200 ?30 ?1000 ?100 ?4 ?16．1 ?57
?200 ?30 ?1000 ?100 ?5 ?16．1 ?57
?200 ?30 ?1000 ?100 ?6 ?25．1 ?58
mp：68-70℃／18mmHg；
1HNMRδ：7．50-7．97ppm：
19FNMR δ: φ-45.03ppm (s); Ultimate analysis C 8H 4Cl 2F 4:
Calculated value: C:38.90; H:1.63; Cl:28.70; F:30.76.
Measured value: C:38.85; H:1.59; Cl:28.75; F:30.80.
Embodiment 5
With the 200g raw material Be connected to liquid-phase tube, condenser, churned mechanically reactor with 50g catalyzer-perfluor sulfonyl fluorine adding, liquid-phase tube links to each other with the HF steel cylinder, valve and surge flask are arranged between reactor and the steel cylinder, the HF steel cylinder places 80 ℃ of hot water baths, and surge flask places 110 ℃ of oil baths, after reactor is heated to 100 ℃, begin to stir, and open cylinder valve and begin logical HF, after reaction finishes, valve-off.After reactor is cooled to room temperature, add the diluted alkaline neutralization, take out reaction mixture, tell organic phase after the washing, drying, underpressure distillation gets product
Figure 9710679000101
, actual conditions and result are as follows:
Reaction times (hour) 7 ?7 ?7 ?7 ?7 ?7 ?7
?R fSO 2F，Rf= C nF 2n+1， n=2 ?n=3 n=4 ?n=6 n=8 ?n=10 ?n=12
?HF(g) 14 ?31 ?50 ?67 ?81 ?93 ?107
Productive rate % 17 ?19 ?11 ?27 ?45 ?63 ?51
mp：64-65℃／18mmHg；
1HNMRδ：7．73ppm(s)；
19FNMR δ: φ-50.4ppm (s); Ultimate analysis C 8H 4Cl 2F 4:
Calculated value: C:38.90; H:1.63; Cl:28.70; F:30.76.
Measured value: C:38.93; H:1.66; Cl:28.77; F:30.73.
Embodiment 6
With raw material
Figure 9710679000102
Drop in 21 autoclaves of inner liner polytetrafluoroethylene cover with fluorination reagent, close the reaction of autoclave post-heating.Reaction finishes postcooling, opens autoclave, takes out reaction mixture, and suction filtration is removed fluorination reagent, uses CH 2Cl 2* 3 washings are adsorbed superincumbent product to reclaim, merging filtrate, washings, and normal 0 presses distillation to remove CH 2Cl 2, underpressure distillation gets product again Actual conditions and result are as follows:
Raw material (g) Fluorination reagent Catalyzer Temperature of reaction (℃) Reaction times (h) Pressure (atm) Productive rate (%)
200 ?CsF-CaF ?C 5F 11SO 2F ?120 ?4 ?1．1 ?38
?200 ?KF-CaF 18 hats-6 ?160 ?12 ?1．4 ?21
200 ?NaF-CaF ?C 7F 15SO 2F ?220 ?25 ?1．9 ?9
200 ?CsF ?C 9F 19SO 2F ?140 ?6 ?1．2 ?15
?200 ?KF 18 hats-6 ?180 ?15 ?1．7 ?6
?200 ?NaF ?C 11F 23SO 2F ?220 ?30 ?2．1 ?3．2
The experimental data of compound is with embodiment 5.

Claims (8)

1. one kind prepares a class α, and the method for α '-fluorine halogen substituted dimethyl benzene is characterized in that with ortho position or contraposition
Figure 9710679000021
Be raw material, wherein X=Br or Cl, at catalyzer or catalyst-free, solvent or do not have solvent, under normal pressure-30atm pressure condition, with fluorination reagent 40-220 ℃ of 0.5-30 hour synthetic corresponding ortho position of reaction or contraposition down X=Br or Cl, wherein
Figure 9710679000023
The mol ratio of fluorination reagent and catalyzer is: 1: 4: 0.1-1: 20: 1.
2. preparation one class α as claimed in claim 1, the method of α '-fluorine halogen substituted dimethyl benzene, it is characterized in that fluorination reagent is hydrogen fluoride or fluorine anion reagent, wherein fluorine anion reagent is Sodium Fluoride, Potassium monofluoride, cesium fluoride, Sodium Fluoride-Calcium Fluoride (Fluorspan), Potassium monofluoride-Calcium Fluoride (Fluorspan), cesium fluoride-Calcium Fluoride (Fluorspan).
3. preparation one class α α as claimed in claim 1, the method for α '-fluorine halogen substituted dimethyl benzene, used catalyzer is SbCl in it is characterized in that synthesizing 5, 18 the hat-6, R fSO 2F, wherein Rf=C nF 2nt, n=2-12.
4. preparation one class α as claimed in claim 1, the method of α '-fluorine halogen substituted dimethyl benzene is characterized in that solvent is Skellysolve A, normal hexane, hexanaphthene, sherwood oil, methylene dichloride, trifluoromethane, tetracol phenixin, tetrahydrofuran (THF), ether, acetonitrile, benzene,toluene,xylene, pyridine, triethylamine, fluorochlorohydrocarbon and surrogate thereof.
5. preparation one class α as claimed in claim 1, the method for α '-fluorine halogen substituted dimethyl benzene is characterized in that
Figure 9710679000024
The mol ratio of fluorination reagent and catalyzer is 1: 4: 0.1-1: 10: 0.5.
6. preparation one class α as claimed in claim 1, the method for α '-fluorine halogen substituted dimethyl benzene is characterized in that reaction pressure is 10-20atm.
7. preparation one class α as claimed in claim 1, the method for α '-fluorine halogen substituted dimethyl benzene is characterized in that temperature of reaction is 70-120 ℃.
8. preparation one class α as claimed in claim 1, the method for α '-fluorine halogen substituted dimethyl benzene is characterized in that the reaction times is 3-6 hour.
CN97106790A 1997-12-22 1997-12-22 Method for prepn. of a, a'-fluorohalogenated xylene Expired - Fee Related CN1060462C (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN97106790A CN1060462C (en) 1997-12-22 1997-12-22 Method for prepn. of a, a'-fluorohalogenated xylene

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN97106790A CN1060462C (en) 1997-12-22 1997-12-22 Method for prepn. of a, a'-fluorohalogenated xylene

Publications (2)

Publication Number Publication Date
CN1184799A CN1184799A (en) 1998-06-17
CN1060462C true CN1060462C (en) 2001-01-10

Family

ID=5169000

Family Applications (1)

Application Number Title Priority Date Filing Date
CN97106790A Expired - Fee Related CN1060462C (en) 1997-12-22 1997-12-22 Method for prepn. of a, a'-fluorohalogenated xylene

Country Status (1)

Country Link
CN (1) CN1060462C (en)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5125000A (en) * 1974-08-23 1976-02-28 Tonichi Seisakusho Kk PURISETSUTOGATATORUKURENCHI
JPS5140012A (en) * 1974-09-30 1976-04-03 Shimazu Denki Keisokuki Kk Denwakaisen no wachuuhindosokuteisoochi
CN1080278A (en) * 1992-06-17 1994-01-05 中国科学院长春应用化学研究所 The preparation method of monochloro-o-dimethyl benzene

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5125000A (en) * 1974-08-23 1976-02-28 Tonichi Seisakusho Kk PURISETSUTOGATATORUKURENCHI
JPS5140012A (en) * 1974-09-30 1976-04-03 Shimazu Denki Keisokuki Kk Denwakaisen no wachuuhindosokuteisoochi
CN1080278A (en) * 1992-06-17 1994-01-05 中国科学院长春应用化学研究所 The preparation method of monochloro-o-dimethyl benzene

Also Published As

Publication number Publication date
CN1184799A (en) 1998-06-17

Similar Documents

Publication Publication Date Title
KR100284250B1 (en) Process for producing 1,1,1,3,3-pentafluoropropane
CN1902152A (en) Process for producing fluoropropenes
CN1968915A (en) Processes for synthesis of 1,3,3,3-tetrafluoropropene
CN1051252C (en) Catalyst production
CN1328537A (en) Method of producing acyl fluorides from acyl chlorides
CN1511135A (en) Process of preparing halogenated esters
CN101052616A (en) Method for producing fluorine-containing fluorosulfonyl alkylvinyl ether
JP4230220B2 (en) Method for producing substituted phenylacetonitrile
CN107790186B (en) Novel decamethyl cyclopentadienyl zirconium complex and preparation method and application thereof
CN1060462C (en) Method for prepn. of a, a'-fluorohalogenated xylene
JP3522554B2 (en) Method for C-alkylating malonic acid dialkyl esters
US7119232B2 (en) Nucleophilic substitution reactions of difluorormethyl phenyl sulfone with alkyl halides leading to the facile synthesis of terminal 1,1-difluoro-1-alkenes and difluoromethylalkanes
CN1125027C (en) Process for producing di-tert-butyl dicarbonate
CN1174948C (en) Method for preparing perfluoroethyl
CN1215041C (en) Method for preparing polyhalogenated paratriefluoromethylanilines
CN1121371C (en) Continuous process for preparation of pivaloyl chloride and of aroyl chloride
CN1280268C (en) Process for producing bishalophenyl disulfide
JP4719446B2 (en) Method for producing dl-1,2-diphenylethylenediamine
JP3503150B2 (en) Method for producing 4-phenyl-1-butenes
JP3270571B2 (en) Method for producing allyl bromide
JP3174968B2 (en) Method for producing 2-halogeno-6-substituted thiobenzonitrile
US8258362B2 (en) Method for the production of α, ω-olefins by using the copper catalyzed coupling reaction of a Grignard reagent with an allylic substrate
JP2023058407A (en) Method for producing p-phenylene diamine
JPH0739359B2 (en) Process for producing dichloro- (2,2) -paracyclophane
JP3234766B2 (en) Method for producing sulfonic acid halide

Legal Events

Date Code Title Description
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C06 Publication
PB01 Publication
C14 Grant of patent or utility model
GR01 Patent grant
C19 Lapse of patent right due to non-payment of the annual fee
CF01 Termination of patent right due to non-payment of annual fee